EP4090715A1 - Sealing tape bonding weakly or not at all on one side - Google Patents

Sealing tape bonding weakly or not at all on one side

Info

Publication number
EP4090715A1
EP4090715A1 EP21702168.2A EP21702168A EP4090715A1 EP 4090715 A1 EP4090715 A1 EP 4090715A1 EP 21702168 A EP21702168 A EP 21702168A EP 4090715 A1 EP4090715 A1 EP 4090715A1
Authority
EP
European Patent Office
Prior art keywords
polymer foam
foam layer
adhesive tape
weight
adhesive
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP21702168.2A
Other languages
German (de)
French (fr)
Inventor
Li Wang
Deniz Nick Akin
Kim ELSENBACH
Hannes DAG
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tesa SE
Original Assignee
Tesa SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Tesa SE filed Critical Tesa SE
Publication of EP4090715A1 publication Critical patent/EP4090715A1/en
Pending legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00Adhesives in the form of films or foils
    • C09J7/20Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22Plastics; Metallised plastics
    • C09J7/26Porous or cellular plastics
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00Adhesives in the form of films or foils
    • C09J7/10Adhesives in the form of films or foils without carriers
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00Adhesives in the form of films or foils
    • C09J7/20Adhesives in the form of films or foils characterised by their carriers
    • C09J7/29Laminated material
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00Adhesives in the form of films or foils
    • C09J7/30Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38Pressure-sensitive adhesives [PSA]
    • C09J7/381Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/385Acrylic polymers
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/346Applications of adhesives in processes or use of adhesives in the form of films or foils for building applications e.g. wrap foil
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00Additional features of adhesives in the form of films or foils
    • C09J2301/20Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive itself
    • C09J2301/208Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive itself the adhesive layer being constituted by at least two or more adjacent or superposed adhesive layers, e.g. multilayer adhesive
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00Additional features of adhesives in the form of films or foils
    • C09J2301/30Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/302Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2400/00Presence of inorganic and organic materials
    • C09J2400/20Presence of organic materials
    • C09J2400/24Presence of a foam
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2400/00Presence of inorganic and organic materials
    • C09J2400/20Presence of organic materials
    • C09J2400/24Presence of a foam
    • C09J2400/243Presence of a foam in the substrate
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2423/00Presence of polyolefin
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2423/00Presence of polyolefin
    • C09J2423/006Presence of polyolefin in the substrate
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2433/00Presence of (meth)acrylic polymer
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2433/00Presence of (meth)acrylic polymer
    • C09J2433/006Presence of (meth)acrylic polymer in the substrate
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2453/00Presence of block copolymer
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2453/00Presence of block copolymer
    • C09J2453/006Presence of block copolymer in the substrate

Definitions

  • the invention relates to the technical field of adhesive tapes, as they are often used in households and in industry for joining two substrates, but also for other purposes such as protecting surfaces or for sealing. More specifically, a foam adhesive tape suitable for sealing is proposed which has different adhesive strengths on its two main sides or is provided with pressure-sensitive adhesive on only one of its two main sides.
  • Seals are required for many constructions in different fields of technology, for example in construction and in vehicle construction.
  • the sealing elements used for this purpose should often seal gaps, which are almost inevitable when connecting two components, against the ingress of moisture and air, in order to protect the parts behind them from damage caused by this, e.g. from corrosion.
  • Mechanical connections, such as those made by screws, are usually not able to produce a sufficient seal.
  • silicone sealants for example, are often used in order to achieve a suitable seal for the connections made.
  • Such sealing compounds can be processed quite reliably, but require a certain time to harden and thus often cause process engineering difficulties.
  • the situation is similar with other structural adhesives or sealants, e.g. those based on epoxides or polyurethanes.
  • Silicone foams are also used as sealing compounds; they are characterized by good flame retardant properties and their reusability. On the other hand, it is difficult to process them in an automated process, and they are also comparatively expensive. Butyl sealing compounds are established and inexpensive, on the other hand difficult to control with regard to their dosage and not very resistant to aging. In addition, they are often squeezed out of the gap at higher pressures.
  • Elastic sealants such as rubbers or styrene-butadiene rubbers offer proven sealing properties and are also very temperature-stable. Since they are not self-adhesive, however, their handling is rather difficult; In addition, they are inflexible, so the respective sealing element must fit exactly to the gap to be sealed.
  • Polyurethane foams show good compression behavior and can be processed automatically; so-called foam / n-p / ace applications are also possible. Fluctuations in the dimensions of the foam in question are disadvantageous, and these substances are also susceptible to corrosion and degradation under the influence of certain cleaning agents.
  • EPDM foams show a similar profile of properties; Even with them, only a limited sealing effect can be achieved because of their irregular surface design.
  • WO 2009/086056 A2 describes what is known as a flashing tape, which is intended to exclude moisture in structural applications.
  • the disclosed structure of the tape comprises a viscoelastic core layer and at least one elastomeric outer layer;
  • a pressure-sensitive adhesive layer can be included in order to adhere the tape to a substrate.
  • the object of the invention was therefore to provide a sealing element which is easy to apply and has a high sealing effect against air and moisture and which also offers the possibility of uncomplicated reopening of the sealed gap.
  • a first and general object of the invention is an adhesive tape with different adhesive strength on both main sides, which has a) a polymer foam layer and b) an outer pressure-sensitive adhesive layer and / or an outer thermoplastic film on each side of the polymer foam layer; and is characterized in that, if the adhesive tape comprises an outer pressure-sensitive adhesive layer, it has a higher bond strength on its side equipped with the outer pressure-sensitive adhesive layer than on the opposite side and / or, if the adhesive tape comprises an outer thermoplastic film, it has a lower bond strength on its side equipped with the outer thermoplastic film than on the opposite side.
  • such an adhesive tape can advantageously be used to seal connections between components, on the one hand allowing simple, safe and precise application and on the other hand enabling simple dismantling of the connection.
  • it can be processed automatically and shows a controlled compression behavior.
  • adheresive tape in the context of this invention includes all flat structures with one or both sides self-adhesive, such as films or film sections extended in two dimensions, tapes with extended length and limited width, tape sections, labels, diecuts and the like as well as corresponding multilayer arrangements.
  • a release liner is not part of the adhesive tape, but only an aid for its production and / or storage.
  • the adhesive tape according to the invention comprises a polymer foam layer.
  • a “polymer foam layer” or a “polymer foam” is understood to mean a material with open and / or closed cells distributed over its entire mass, which has a bulk density that is lower than that of the polymeric framework.
  • foam means in particular that the layer in question comprises structures of gas-filled, often spherical or polyhedral cells, which are delimited by liquid, semi-liquid, high viscosity or solid cell webs or their own shell material and which are in such a proportion in the layer in question present that the density of the foamed layer compared to the density of the matrix material, that is to say the entirety of the non-gaseous materials except for any own shell material of the foam cells that may be present.
  • the framework substance also referred to below as polymer foam matrix, foam matrix, matrix or matrix material, is, according to the invention, one or more polymers which can be mixed with additives.
  • Open cells are hollow spaces within the foam that are not completely surrounded by structural substance or a separate shell material.
  • Cells are understood to mean cavities that are completely surrounded by structural substance or a separate shell material.
  • the polymer foam layer of the adhesive tape according to the invention is preferably a closed-cell foam.
  • the polymer foam layer in particular the matrix material of the polymer foam layer, contains at least 35% by weight, more preferably at least 50% by weight and particularly preferably at least 70% by weight, in particular at least 80% by weight, for example at least 90% by weight, based in each case on the total weight of the polymer foam layer or the total weight of the matrix material, of one or more polymers.
  • This polymer content can vary depending on the type of base polymer.
  • Possible polymers of the polymer foam layer include polyolefins, for example polyethylenes such as high density polyethylene (HDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE) and linear ultra low density polyethylene, polypropylene and polybutylene; Vinyl copolymers such as polyvinyl chloride and polyvinyl acetate; olefinic random or block copolymers, e.g.
  • polyethylenes such as high density polyethylene (HDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE) and linear ultra low density polyethylene, polypropylene and polybutylene
  • Vinyl copolymers such as polyvinyl chloride and polyvinyl acetate
  • olefinic random or block copolymers e.g.
  • ethylene-methyl acrylate copolymers ethylene-vinyl acetate copolymers and ethylene-propylene copolymers as well as ethylene-propylene-diene terpolymers (EPDM), also polyalkylenes, which are produced from monomer mixtures, which 1) a first alkene selected from ethylene, propylene or a mixture thereof, and 2) a second alkene selected from 1,2-alkenes having 4 to 8 carbon atoms such as 1,2-butene, 1,2-hexene or 1,2-octene ; Acrylonitrile-butadiene-styrene copolymers; Acrylic polymers and copolymers; Polycarbonates; Polyimides; Polyurethanes, for example thermoplastic polyurethanes, in particular polyester-based thermoplastic polyurethanes; Polyesters, for example polyethylene terephthalate; as well as combinations and blends of the aforementioned polymers.
  • EPDM ethylene-propylene-diene terpolymers
  • Exemplary blends include polypropylene-polyethylene blends, PVC-nitrile rubber blends, polyurethane-polyolefin blends, polyurethane-polycarbonate blends and polyurethane-polyester blends. Furthermore, blends of thermoplastic polymers, elastomeric polymers and combinations thereof can be included. Further blends can be styrene-butadiene copolymers, polychloroprene, e.g. neoprene, nitrile rubbers, butyl rubbers, polysulfide rubbers, cis-1,4-polyisoprene, ethylene-propylene terpolymers, e.g. EPDM rubber, silicone rubbers, Silicone-polyurea block copolymers, polyurethane rubbers, natural rubbers,
  • thermoplastic rubbers e.g. styrene-butadiene block copolymers, styrene-isoprene-styrene block copolymers, styrene-ethylene / butylene-styrene block copolymers,
  • Styrene-ethylene / propylene-styrene block copolymers Styrene-ethylene / propylene-styrene block copolymers, thermoplastic polyolefin rubbers, and combinations thereof.
  • the polymer or polymers of the polymer foam layer are preferably selected from the group consisting of polyolefins; Polyurethanes; Polyvinyl chloride (PVC); Blends of PVC and nitrile rubber; Terpolymers of ethylene, propylene and a non-conjugated diene (EPDM); Copolymers of ethylene and an ethylene substituted with a polar group; Blends of polyethylene and a polymer of an ethylene substituted with a polar group; Poly (meth) acrylates; Blends of poly (meth) acrylate and synthetic rubber and mixtures of two or more of the aforementioned polymers.
  • the polymer foam layer in particular the matrix material of the polymer foam layer, thus preferably contains at least 35% by weight, more preferably at least 50% by weight and particularly preferably at least 70% by weight, in particular at least 80% by weight, for example at least 90% by weight, based in each case on the total weight of the polymer foam layer or the total weight of the matrix material, one or more polymers selected from the group consisting of polyolefins; Polyurethanes; Polyvinyl chloride (PVC); Blends of PVC and nitrile rubber; Terpolymers of ethylene, propylene and a non-conjugated diene (EPDM); Copolymers of ethylene and an ethylene substituted with a polar group; Blends of polyethylene and a polymer of an ethylene substituted with a polar group; Poly (meth) acrylates; Blends of poly (meth) acrylate and synthetic rubber and mixtures of two or more of the aforementioned polymers.
  • polyolefins Polyurethane
  • the matrix material of the polymer foam layer particularly preferably contains no further polymers apart from one or more polymers selected from the group consisting of polyolefins; Polyurethanes; Polyvinyl chloride (PVC); Blends of PVC and nitrile rubber; Terpolymers of ethylene, propylene and a non-conjugated diene (EPDM); Copolymers of ethylene and an ethylene substituted with a polar group; Blends of polyethylene and a polymer of an ethylene substituted with a polar group; Poly (meth) acrylates; Blends of poly (meth) acrylate and synthetic rubber and mixtures of two or more of the aforementioned polymers.
  • polymers selected from the group consisting of polyolefins; Polyurethanes; Polyvinyl chloride (PVC); Blends of PVC and nitrile rubber; Terpolymers of ethylene, propylene and a non-conjugated diene (EPDM); Copolymers of ethylene
  • a “polyolefin” is a polymer of general structure
  • the polyolefin is preferably polyethylene, polypropylene, polybutylene or a mixture of these.
  • the polyethylene can be one or more of the polyethylene types known per se, such as HDPE, LDPE, LLDPE, VLDPE, VLLDPE, MDPE (medium-density PE), metallocene PE types such as mLLDPE and mHDPE, blends of these types of polyethylene and mixtures of which include.
  • the polypropylene is preferably a crystalline polypropylene, more preferably a homopolypropylene (hPP).
  • hPP homopolypropylene
  • the matrix material of the polymer foam layer does not contain any further polymers apart from one or more polyolefins.
  • a copolymer of ethylene and an ethylene substituted by a polar group is understood to mean a polymer of the general structure - [CH2-CR3R4 -] n-, where R3 or R4 denote a hydrogen atom and the remaining substituent denotes a group containing at least one oxygen atom.
  • the copolymer of ethylene and an ethylene substituted by a polar group is preferably an ethylene-vinyl acetate copolymer (EVA), an ethylene-methyl acrylate copolymer (EMA), an ethylene-ethyl acrylate copolymer (EEA), an ethylene-acrylic acid copolymer (EAA), an ethylene-butyl acrylate copolymer (EBA) or a mixture of these.
  • EVA ethylene-vinyl acetate copolymer
  • EMA ethylene-methyl acrylate copolymer
  • EAA ethylene-ethyl acrylate copolymer
  • EAA ethylene-acrylic acid copolymer
  • EBA ethylene-butyl acrylate copolymer
  • the EVA preferably has a vinyl acetate content of 1 to 70% by weight, more preferably 3 to 30% by weight, in particular 5 to 20% by weight.
  • the matrix material of the polymer foam layer contains no further polymers apart from one or more copolymers of ethylene and an ethylene substituted by a polar group.
  • the copolymer of ethylene and an ethylene substituted by a polar group is an ethylene-vinyl acetate copolymer (EVA).
  • the matrix material of the polymer foam layer particularly preferably contains at least one ethylene-vinyl acetate copolymer (EVA).
  • the proportion of all ethylene-vinyl acetate copolymers in the matrix material of the polymer foam layer is at least 50% by weight, more preferably at least 70% by weight and particularly preferably at least 80% by weight, in particular at least 85% by weight, for example at least 90% by weight, based in each case on the total weight of the matrix material.
  • the matrix material very particularly preferably contains no further polymers apart from one or more ethylene-vinyl acetate copolymers (EVA).
  • the matrix material of the polymer foam layer is preferably crosslinked.
  • the crosslinking takes place preferably before the matrix material is foamed.
  • Matrix materials which contain polymers selected from polyolefins and copolymers of ethylene and an ethylene substituted with a polar group are preferably crosslinked with electron beams.
  • Chemical crosslinking methods are also possible, for example crosslinking via grafted silane residues with hydrolyzable groups, which are then influenced by Moisture and catalysis can react with one another; furthermore crosslinking via added silanes which contain a free-radically polymerizable double bond and can react with free radicals which are formed in the polymer chains; as well as crosslinking via added peroxides, which also react with radicals.
  • the polymer foam layer in particular the matrix material of the polymer foam layer, contains at least one poly (meth) acrylate.
  • a “poly (meth) acrylate” is understood to mean a polymer which can be obtained by free-radical polymerization of acrylic and / or methacrylic monomers and optionally other copolymerizable monomers.
  • a “poly (meth) acrylate” is understood to mean a polymer whose monomer base consists of at least 50% by weight of acrylic acid, methacrylic acid, acrylic acid esters and / or methacrylic acid esters, acrylic acid esters and / or methacrylic acid esters at least proportionally, preferably at least 30% by weight .-%, based on the total monomer base of the polymer in question, are included.
  • the polymer foam layer preferably contains a total of 40 to 99.9% by weight of poly (meth) acrylates, more preferably a total of 60 to 98% by weight, in particular a total of 75 to 95% by weight, for example a total of 80 to 90% by weight % By weight, based in each case on the total weight of the polymer foam layer. It can contain a (single) poly (meth) acrylate or several poly (meth) acrylates; The plural term “poly (meth) acrylates” thus includes - also in the continuation of the present description - in its meaning as well as the expression “as a whole” both the presence of a single poly (meth) acrylate and the presence of several poly (meth) acrylates .
  • the glass transition temperature of the poly (meth) acrylates is preferably ⁇ 0 ° C, more preferably between -20 and -50 ° C.
  • the glass transition temperature of polymers or of polymer blocks in block copolymers is determined according to the invention by means of dynamic scanning calorimetry (DSC). For this purpose, approx. 5 mg of an untreated polymer sample are weighed into a small aluminum crucible (volume 25 ml) and closed with a perforated lid. A DSC 204 F1 from Netzsch is used for the measurement. It is carried out under nitrogen for the purpose of inerting.
  • the sample is first cooled to -150 ° C, then heated to +150 ° C at a heating rate of 10 K / min and then cooled again to -150 ° C.
  • the subsequent second heating curve is run again at 10 K / min and the change in heat capacity is recorded. Glass transitions are recognized as steps in the thermogram.
  • the poly (meth) acrylate preferably contains at least one partially polymerized functional monomer, particularly preferably reactive with epoxy groups with the formation of a covalent bond.
  • the proportionately polymerized functional monomer particularly preferably reactive with epoxy groups with formation of a covalent bond, contains at least one functional group selected from the group consisting of carboxylic acid groups, sulfonic acid groups, phosphonic acid groups, hydroxyl groups, acid anhydride groups, epoxy groups and amino groups; in particular it contains at least one carboxylic acid group.
  • the poly (meth) acrylate very preferably contains acrylic acid and / or methacrylic acid which has been partially polymerized into it. All of the groups mentioned have a reactivity with epoxy groups, as a result of which the poly (meth) acrylate is advantageously accessible to thermal crosslinking with introduced epoxides.
  • the poly (meth) acrylate can preferably be attributed to the following monomer composition: a) at least one acrylic acid ester and / or methacrylic acid ester of the following formula (1)
  • Group selected from the group consisting of carboxylic acid groups, sulfonic acid groups, phosphonic acid groups, hydroxyl groups,
  • Acid anhydride groups, epoxy groups and amino groups c) optionally further acrylic acid esters and / or methacrylic acid esters and / or olefinically unsaturated monomers which are copolymerizable with component (a).
  • the monomers of component a) in a proportion of 45 to 99% by weight, the monomers of component b) in a proportion of 1 to 15% by weight and the monomers of component c) in a proportion from 0 to 40% by weight to be selected, the information being based on the monomer mixture for the base polymer without the addition of any additives such as resins, etc.
  • the poly (meth) acrylate can particularly preferably be attributed to the following monomer composition:
  • the poly (meth) acrylate or the poly (meth) acrylates are preferably prepared by conventional free-radical polymerizations or controlled free-radical polymerizations.
  • the poly (meth) acrylates can be prepared by copolymerizing the monomers using customary polymerization initiators and, if appropriate, regulators, polymerizing at the customary temperatures in bulk, in emulsion, for example in water or liquid hydrocarbons, or in solution.
  • the poly (meth) acrylates are preferred by copolymerizing the monomers in solvents, particularly preferably in solvents with a boiling range from 50 to 150 ° C., in particular from 60 to 120 ° C., using 0.01 to 5% by weight, in particular from 0.1 to 2% by weight, based in each case on the total weight of the monomers, of polymerization initiators.
  • radical sources are peroxides, hydroperoxides and azo compounds, for example dibenzoyl peroxide, cumene hydroperoxide, cyclohexanone peroxide, di-t-butyl peroxide, cyclohexylsulfonylacetyl peroxide,
  • Preferred free-radical initiators are 2,2'-azobis (2-methylbutyronitrile) (Vazo® 67 TM from DuPont) or 2,2'-azobis (2-methylpropionitrile) (2,2'-azobisisobutyronitrile; AIBN; Vazo® 64 TM from DuPont).
  • Preferred solvents for the preparation of the poly (meth) acrylates are alcohols such as methanol, ethanol, n- and iso-propanol, n- and iso-butanol, in particular isopropanol and / or isobutanol; Hydrocarbons such as toluene and, in particular, gasolines with a boiling range from 60 to 120 ° C .; Ketones, especially acetone, methyl ethyl ketone, methyl isobutyl ketone; Esters such as ethyl acetate and mixtures of the abovementioned solvents.
  • Particularly preferred solvents are mixtures which contain isopropanol in amounts of from 2 to 15% by weight, in particular from 3 to 10% by weight, based in each case on the solvent mixture used.
  • the concentration is essentially solvent-free.
  • the polymer can be concentrated in the absence of crosslinking and accelerating substances.
  • the polymers can be transferred to a compounder. If necessary, the concentration and the compounding can also take place in the same reactor. Further processing after the concentration (Compounding) takes place preferably in one or more extruders.
  • the mass is applied from the melt to an optionally temporary carrier material and formed into a layer by means of calender rollers.
  • the weight-average molecular weights M w of the poly (meth) acrylates are preferably in a range from 20,000 to 2,000,000 g / mol; very preferably in a range from 100,000 to 1,500,000 g / mol, extremely preferably in a range from 150,000 to 1,000,000 g / mol.
  • suitable polymerization regulators such as thiols, halogen compounds and / or alcohols in order to set the desired average molecular weight.
  • the details of the number-average molar mass M n and the weight-average molar mass M w in this document relate to the known determination by gel permeation chromatography (GPC). The determination is carried out on 100 ml clear-filtered sample (sample concentration 4 g / l). Tetrahydrofuran with 0.1% by volume of trifluoroacetic acid is used as the eluent. The measurement takes place at 25 ° C.
  • a combination of columns of the PSS-SDV, 5 pm, 10 3 ⁇ , as well as 10 5 ⁇ and 10 6 ⁇ , each 8.0 mm * 300 mm, is used for separation (columns from Polymer Standards Service; detection using a Shodex RI71 differential refractometer ). The flow rate is 1.0 ml per minute.
  • PMMA standards polymethyl methacrylate calibration
  • resins, elastomers polystyrene calibration
  • the poly (meth) acrylate preferably has a polydispersity PD ⁇ 4 and thus a relatively narrow molecular weight distribution.
  • compositions based thereon have a particularly good shear strength after crosslinking.
  • the lower polydispersity enables easier processing from the melt, since the flow viscosity is lower than that of a more widely distributed poly (meth) acrylate with largely the same application properties.
  • Narrowly distributed poly (meth) acrylates can advantageously be prepared by anionic polymerization or by controlled radical polymerization methods, the latter being particularly suitable.
  • Corresponding poly (meth) acrylates can also be produced via N-oxyls.
  • atom transfer radical polymerization can advantageously be used for the synthesis of narrowly distributed poly (meth) acrylates, the initiator preferably being monofunctional or difunctional secondary or tertiary halides and, for the abstraction of the halides, Cu, Ni, Fe, Pd, Pt, Ru, Os-, Rh-, Co-, Ir-, Ag- or Au complexes can be used.
  • RAFT polymerization is also suitable.
  • the poly (meth) acrylates are preferably crosslinked by linking reactions - in particular in the sense of addition or substitution reactions - of functional groups contained in them with thermal crosslinkers. All thermal crosslinkers can be used that
  • Thermal crosslinkers are preferably used in an amount of from 0.1 to 5% by weight, in particular from 0.2 to 1% by weight, based on the total amount of the polymer to be crosslinked.
  • Crosslinking via complexing agents is also possible.
  • a preferred complexing agent is, for example, aluminum acetylacetonate.
  • the poly (meth) acrylates are preferably crosslinked by means of epoxide (s) or by means of one or more substance (s) containing epoxide groups.
  • the substances containing epoxy groups are in particular multifunctional epoxides, that is to say those with at least two epoxy groups; accordingly, overall there is an indirect linkage of the building blocks of the poly (meth) acrylates which carry the functional groups.
  • the substances containing epoxy groups can be both aromatic and aliphatic compounds.
  • Preferred epoxy crosslinkers are, for example, cycloaliphatic epoxides such as 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (UVACure1500).
  • the poly (meth) acrylates are particularly preferably crosslinked by means of a crosslinker-accelerator system (“crosslinking system”) in order to obtain better control over the processing time, the crosslinking kinetics and the degree of crosslinking.
  • the crosslinker-accelerator system preferably comprises at least one substance containing epoxy groups as crosslinker and at least one substance that accelerates crosslinking reactions by means of compounds containing epoxy groups at a temperature below the melting temperature of the polymer to be crosslinked.
  • the polymer foam layer in particular the matrix material of the polymer foam layer, contains at least one vinyl aromatic block copolymer.
  • the polymer foam layer, in particular the matrix material of the polymer foam layer preferably contains at least one vinyl aromatic block copolymer which contains at least one polymer block A which is predominantly formed by the polymerization of vinyl aromatic compounds and at least one polymer block B which is predominantly formed by the polymerization of conjugated dienes, the The proportion of 1,2-linked conjugated diene in the B block is less than 30% by weight, preferably less than 20% by weight (can be determined by means of 1 H-NMR).
  • the vinyl aromatic block copolymer described above is preferably contained in the polymer foam as an elastomer component in embodiment III considered here. If the polymer foam contains several elastomer components, it is preferably contained in the polymer foam to an extent of at least 50% by weight, based on the total weight of all elastomer components.
  • the polymer block A of the preferred vinyl aromatic block copolymer is formed predominantly by the polymerization of vinyl aromatic compounds. This means that the block A typically emerged from a polymerization in which more than 50% by weight of the monomers used are vinyl aromatics. More preferably, the polymer block A emerged from a polymerization in which exclusively vinyl aromatics were used as monomers.
  • the polymer block B of the preferred vinyl aromatic block copolymer is formed predominantly by the polymerization of conjugated dienes. This means that block B emerged from a polymerization in which more than 50% by weight of the monomers used are conjugated dienes. More preferably, the polymer block B emerged from a polymerization in which exclusively conjugated dienes were used as monomers.
  • the proportion of 1,2-linked conjugated diene in the B block of the preferred vinyl aromatic block copolymer is less than 30% by weight, preferably less than 20% by weight. This proportion is more preferably less than 15% by weight, in particular 8 to 12% by weight.
  • the proportion of 1,2-linked conjugated diene in the B block is the proportion by weight of conjugated diene which has been polymerized by 1,2 addition (as opposed to 1,4 addition), based on the Production of the polymer block B total monomer mass used.
  • the 1,2 addition of conjugated diene results in a vinylic side group in the polymer block B, while the 1,4-addition of conjugated diene leads to a vinylic functionality in the main chain of the polymer block B.
  • the 1,2 addition of a conjugated diene thus means that the incorporation of the monomer into the polymer chain takes place either via positions C1 and C2 or via positions C3 and C4 (for example in the case of isoprene as conjugated diene).
  • the 1,4-addition of a conjugated diene on the other hand, it runs through positions C1 and C4.
  • the vinyl aromatic block copolymer preferably has a structure AB, ABA, (AB) n , (AB) n X or (ABA) nX, in which the blocks A independently of one another for a polymer formed by polymerization of at least one vinyl aromatic, the blocks B independently of one another for a polymer formed by the polymerization of conjugated dienes with 4 to 18 carbon atoms,
  • X stands for the remainder of a coupling reagent or initiator and n stands for an integer> 2.
  • Particularly preferred in embodiment III are all vinyl aromatic block copolymers of the polymer foam layer according to the invention block copolymers with a structure AB, ABA, (AB) n, (AB) nX or (ABA) n X as set out above.
  • the polymer foam layer can thus also contain mixtures of different vinyl aromatic block copolymers with a structure as described above.
  • the blocks B are also referred to as rubber-like blocks or soft blocks and the blocks A as glass-like blocks or hard blocks.
  • at least one vinyl aromatic block copolymer of the polymer foam layer has a structure AB, ABA, (AB) 2X, (AB) 3X or (AB) 4 X, where A, B and X are as defined above.
  • All vinylaromatic block copolymers very particularly preferably have a structure AB, ABA, (AB) 2X, (AB) 3X or (AB) 4 X, where A, B and X are as defined above.
  • the polymer foam layer contains a mixture of block copolymers with a structure AB, ABA, (AB) 2X, (AB) sX or (AB) 4 X, which is more preferably at least diblock copolymers AB and / or triblock copolymers ABA and / or ( AB) 2X contains, in particular, a mixture of diblock copolymers (AB) and triblock copolymers (ABA), for example of two types of vinyl aromatic block copolymers with a different weight ratio of diblock copolymers (AB) and triblock copolymers (ABA).
  • AB diblock copolymers
  • ABA triblock copolymers
  • the vinyl aromatic block copolymers preferably have a diblock copolymer content of 0% by weight to 70% by weight, more preferably from 15% by weight to 65% by weight, in particular from 30 to 60% by weight, very particularly preferably from 40 to 60% by weight, for example from 51.5% by weight to 55% by weight.
  • the block copolymers resulting from the A and B blocks can contain the same or different B blocks.
  • the proportion of polyvinyl aromatics, in particular of polystyrene is preferably at least 12% by weight, more preferably at least 18% by weight, particularly preferably at least 25% by weight and also preferably at most 45% by weight % and more preferably at most 35% by weight.
  • polymer blocks based on other aromatic-containing homopolymers and copolymers with glass transition temperatures of greater than 75 ° C. can also be used as vinyl aromatics.
  • the polymer block A is preferably formed predominantly by the polymerization of styrene and / or ⁇ -methylstyrene.
  • the block A can thus be present as a homo- or copolymer.
  • Block A is particularly preferably a polystyrene.
  • the vinyl aromatic block copolymers very particularly preferably have polystyrene end blocks.
  • the polymer block B is preferably formed predominantly by polymerization of conjugated dienes selected from the group consisting of butadiene, isoprene, ethylbutadiene, phenylbutadiene, pentadiene, hexadiene, ethylhexadiene, dimethylbutadiene, ⁇ -farneses and ⁇ -farneses and any mixtures of these monomers; like block A, it can be present as a homopolymer or as a copolymer.
  • Block B is particularly preferably formed predominantly by polymerizing butadiene and / or isoprene.
  • Block B is very particularly preferably a polybutadiene; this shows an even better aging behavior compared to polyisoprene.
  • a blocks are also referred to as “hard blocks” in the context of this invention.
  • B blocks are also called “soft blocks” or “elastomer blocks”. This reflects the selection of the blocks according to their glass transition temperatures, which for the A blocks is preferably at least 25 ° C., in particular at least 50 ° C., and for B blocks is preferably at most 25 ° C, particularly preferably at most -25 ° C, and in particular at most -50 ° C.
  • the proportion of all the vinyl aromatic block copolymers, in particular the styrene block copolymers, in the polymer foam layer is preferably at least 35% by weight, based on the total weight of the polymer foam layer. Such a proportion advantageously improves the cohesion of the polymer foam layer.
  • the maximum proportion of all of the vinyl aromatic block copolymers, in particular the styrene block copolymers, in the polymer foam layer is preferably a maximum of 75% by weight, in particular a maximum of 65% by weight, very particularly preferably a maximum of 55% by weight.
  • the polymer foam of embodiment III preferably contains at least one adhesive resin.
  • one or more tackifier resins can be included. In this way, the foam is advantageously given pressure-sensitive adhesive properties.
  • an “adhesive resin” is understood to mean a low molecular weight, oligomeric or polymeric resin which increases the adhesion (the tack, the inherent tack) of the PSA in comparison to the PSA which does not contain adhesive resin but is otherwise identical.
  • the adhesive resin preferably has a DACP (diacetone alcohol cloud point) of> 0 ° C, more preferably> 10 ° C, in particular> 30 ° C, and a softening temperature (ring & ball) of> 70 ° C, preferably> 100 ° C.
  • DACP diacetone alcohol cloud point
  • the respective adhesive resin particularly preferably has a DACP value of a maximum of 45 ° C. if there are no isoprene blocks in the elastomer phase, or of a maximum of 60 ° C. if there are isoprene blocks in the elastomer phase.
  • the softening temperature of the respective adhesive resin is particularly preferably a maximum of 150.degree.
  • the adhesive resin is a hydrocarbon resin;
  • it is selected from the group consisting of hydrogenated and non-hydrogenated polymers of dicyclopentadiene, non-hydrogenated, partially, selectively or fully hydrogenated hydrocarbon resins based on C5, C5 / C9 or C9 monomer streams and polyterpene resins based on a-pinene and / or ß-pinene and / or d-limonene.
  • tackifier resins can be used either alone or as a mixture. In principle, both solid and liquid resins can be used at room temperature.
  • Adhesive resins hydrogenated or non-hydrogenated, which also contain oxygen, can optionally contain up to a maximum proportion of 25% by weight, based on the total mass of the adhesive resins contained in the polymer foam, in the polymer foam of embodiment III such as rosin and / or rosin ester resins and / or terpene phenolic resins.
  • the adhesive resin is particularly preferably a non-hydrogenated hydrocarbon resin, in particular based on ⁇ -pinene.
  • these resins advantageously also give the polymer foam a very high level of adhesion, in particular even at high temperatures.
  • the polymer foam of embodiment III preferably contains 20 to 60% by weight, particularly preferably 30 to 50% by weight, based in each case on the total weight of the polymer foam, of at least one adhesive resin.
  • foams can be produced in two ways: on the one hand by the action of a propellant gas, either added as such or resulting from a chemical reaction, on the other hand by incorporating hollow spheres into the material matrix. Foams made in the latter way are known as syntactic foams.
  • Physical blowing agents are any naturally occurring atmospheric material that is gaseous at the temperature and pressure at which the foam emerges from the nozzle. Physical propellants can be introduced, ie injected, into the matrix material as a gas, as a supercritical fluid or as a liquid. The choice of physical blowing agent used depends on the desired properties of the resulting foams. Other factors to consider when choosing a blowing agent are its toxicity, vapor pressure profile, ease of handling, and solubility with respect to the polymeric materials used.
  • Flammable propellants such as pentane, butane, and other organic materials such as fluorocarbons and chlorofluorocarbons can be used; however, preference is given to non-flammable, non-toxic, non-ozone-depleting propellants because they are easier to use, there are fewer concerns about their effects on the environment, etc.
  • Preferred physical propellants are carbon dioxide, nitrogen, SF6, nitrogen oxides, perfluorinated liquids such as C2F6, noble gases such as Helium, argon and xenon, air (typically a mixture of nitrogen and oxygen), and mixtures of these materials.
  • chemical blowing agents can also be used for foaming.
  • Suitable chemical propellants include mixtures of sodium bicarbonate and citric acid, dinitrosopentamethylenetetramine, p-toluenesulfonyl hydrazide, 4-4'-oxybis (benzenesulfonylhydrazide, azodicarbonamide (1,1'-azobisformamide), p-toluenesulfonoga-tetyl-tetrazyl-prazole, 5-phenrazyl-analogs , Diisopropyl hydrazodicarboxylate, 5-phenyl-3,6-dihydro-1, 3,4-oxadiazin-2-one and sodium borohydride.
  • the polymer foam layer preferably contains microballoons; in this case it is at least foamed using microballoons. If it is only foamed using microballoons, it is a syntactic foam.
  • Microballoons are understood to mean elastic and thus expandable microspheres in their basic state, which have a thermoplastic polymer shell. These balls are filled with low-boiling liquids or liquefied gas.
  • polyacrylonitrile, PVDC, PVC or polyacrylates are used as the shell material.
  • Hydrocarbons of the lower alkanes, for example isobutane or isopentane, which are enclosed as a liquefied gas under pressure in the polymer shell, are particularly common as the low-boiling liquid.
  • the outer polymer shell softens.
  • the liquid propellant in the envelope changes into its gaseous state.
  • the microballoons expand irreversibly and expand three-dimensionally. The expansion is finished when the internal and external pressures equalize. Since the polymer shell is retained, a closed-cell foam is achieved.
  • microballoons are commercially available, which differ essentially in terms of their size (6 to 45 ⁇ m diameter in the unexpanded state) and their starting temperatures (75 to 220 ° C.) required for expansion.
  • Unexpanded types of microballoons are also available as aqueous dispersions with a solids or microballoon content of approx. 40 to 45% by weight, and also as polymer-bound microballoons (masterbatches), for example in ethylene vinyl acetate with a microballoon concentration of approx. 65% by weight. Both the microballoon dispersions and the masterbatches, like the unexpanded microballoons, are suitable as such for producing the polymer foam layer.
  • the polymer foam can also be produced with so-called pre-expanded microballoons. In this group, expansion takes place before it is mixed into the polymer matrix.
  • the polymer foams can also be produced with foamed particles, that is to say with expanded or expandable beads made of, in particular, polystyrene, polypropylene, thermoplastic polyurethane or cellulose acetate, for which the term “beads” has become established. Particles of already foamed plastics are mixed into the polymer matrix, which cause the density to decrease. The particles can also be placed in the polymer matrix without being foamed and only then foamed.
  • the polymer foam can also consist of “beads” thermally connected to one another, in particular welded, possibly pre-expanded, so that in this case no further surrounding matrix is present.
  • the polymer foam can contain anti-aging agents, e.g. primary antioxidants such as sterically hindered phenols, secondary antioxidants such as phosphites or thioethers and / or carbon radical scavengers. It is also possible, for example, to use light stabilizers such as UV absorbers or sterically hindered amines; Antiozonants; Metal deactivators and / or processing aids may be included.
  • anti-aging agents e.g. primary antioxidants such as sterically hindered phenols, secondary antioxidants such as phosphites or thioethers and / or carbon radical scavengers.
  • light stabilizers such as UV absorbers or sterically hindered amines; Antiozonants; Metal deactivators and / or processing aids may be included.
  • the polymer foam can also contain fillers such as silicon dioxide, glass (ground or in the form of spheres), aluminum oxides, zinc oxides, calcium carbonates, titanium dioxide, carbon blacks, etc., as well as pigments, dyes and / or optical brighteners.
  • fillers such as silicon dioxide, glass (ground or in the form of spheres), aluminum oxides, zinc oxides, calcium carbonates, titanium dioxide, carbon blacks, etc., as well as pigments, dyes and / or optical brighteners.
  • a pressure-sensitive adhesive or a pressure-sensitive adhesive is understood, as is customary in common parlance, to be a substance which is permanently tacky and also tacky at least at room temperature. It is characteristic of a pressure-sensitive adhesive that it can be applied to a substrate by pressure and remains adhered there, the pressure to be applied and the duration of this pressure not being defined in more detail. In general, but basically depending on the exact type of pressure-sensitive adhesive as well as the substrate, the temperature and the air humidity, the application of a short-term, minimal pressure, which does not go beyond a light touch for a short moment, is sufficient to achieve the adhesive effect in other cases a longer period of exposure to a higher pressure may be necessary.
  • Pressure-sensitive adhesives have special, characteristic viscoelastic properties which lead to permanent tack and adhesiveness. They are characterized by the fact that when they are mechanically deformed, both viscous flow processes and the build-up of elastic restoring forces occur. Both processes are related to each other in terms of their respective share, depending on the exact one Composition, the structure and the degree of crosslinking of the PSA as well as the speed and duration of the deformation and the temperature.
  • the proportionate viscous flow is necessary to achieve adhesion. Only the viscous components, often caused by macromolecules with relatively high mobility, enable good wetting and flow onto the substrate to be bonded. A high proportion of viscous flow leads to high pressure-sensitive tack (also referred to as tack or surface tack) and thus often also to high adhesion. Strongly cross-linked systems, crystalline or glass-like solidified polymers are generally not or at least only slightly tacky due to the lack of flowable components.
  • the proportional elastic restoring forces are necessary to achieve cohesion. They are caused, for example, by very long-chain and strongly tangled macromolecules as well as by physically or chemically cross-linked macromolecules and enable the forces acting on an adhesive bond to be transmitted. They lead to the fact that an adhesive connection can withstand a permanent load acting on it, for example in the form of permanent shear stress, to a sufficient extent over a longer period of time.
  • G ‘ The storage modulus (G ‘) and loss modulus (G”) that can be determined by means of dynamic mechanical analysis (DMA) are used for a more precise description and quantification of the amount of elastic and viscous components as well as the relationship between the components.
  • G ‘ is a measure for the elastic part
  • G“ is a measure for the viscous part of a substance. Both sizes are dependent on the deformation frequency and the temperature.
  • the sizes can be determined with the aid of a rheometer.
  • the material to be examined is exposed to a sinusoidal oscillating shear stress, for example in a plate-plate arrangement.
  • the deformation is measured as a function of time and the time offset of this deformation with respect to the introduction of the shear stress. This time offset is referred to as the phase angle d.
  • a mass is considered a pressure-sensitive adhesive and is defined as such within the meaning of the invention if at 23 ° C in the deformation frequency range of 10 ° to 10 1 rad / sec both G 'and G ′′ are at least partially in the range of 10 3 up to 10 7 Pa lie. “Partly” means that at least a section of the G 'curve lies within the window that is defined by the deformation frequency range from 10 ° up to and including 10 1 rad / sec (abscissa) and the range of G' values from 10 3 inclusive up to and including 10 7 Pa (ordinate), and if at least a section of the G “curve is also within the corresponding window.
  • the outer pressure-sensitive adhesive layer preferably contains at least 50% by weight, more preferably at least 70% by weight, particularly preferably at least 90% by weight, in particular at least 95% by weight, for example at least 97% by weight , in each case based on the total weight of the pressure-sensitive adhesive layer, one or more
  • the outer pressure-sensitive adhesive layer particularly preferably contains at least 50% by weight, more preferably at least 70% by weight, particularly preferably at least 90% by weight, in particular at least 95% by weight, for example at least 97% by weight %, in each case based on the total weight of the pressure-sensitive adhesive layer, one or more
  • the monomer composition can contain one or more monomers Moni, Mon2 and Mon3, independently of one another.
  • Monomeric moni are preferably at least 70% by weight, more preferably at least 80% by weight, based in each case on the total weight of the
  • Monomeric Mon2 are preferably contained in the monomer composition in an amount of 1 to 15% by weight, based on the total weight of the latter.
  • Monomeric Mon3, if present at all, is preferably present in an amount of 5 to 15% by weight, based on the total weight of the monomer composition.
  • the monomers moni preferably comprise at least one branched monomer.
  • Particularly preferred are the monomers a) selected from the group consisting of n-butyl acrylate, n-butyl methacrylate, n-pentyl acrylate, n-pentyl methacrylate, n-amyl acrylate, n-hexyl acrylate, n-hexyl methacrylate, n-heptyl acrylate, n-octyl acrylate, n -Octyl methacrylate, n-nonylacrylate, isobutyl acrylate, isooctyl acrylate, isooctyl methacrylate, 2-ethylhexyl acrylate and 2-ethylhexyl methacrylate, 2-propylheptyl acrylate and isobornyl acrylate.
  • the monomers Moni are particularly preferably selected from
  • the monomers Mon2 are preferably selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, aconitic acid, dimethylacrylic acid, ⁇ -acryloyloxypropionic acid, trichloroacrylic acid, vinyl acetic acid, vinylphosphonic acid, maleic anhydride, hydroxyhexyl acrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxyhexyl acrylate, hydroxypropyl acrylate, hydroxyhexyl acrylate, hydroxypropyl acrylate, hydroxyhexyl acrylate, hydroxypropyl methacrylate, fumaric acid, crotonic acid, fumaric acid, hydroxyethyl acrylate, hydroxypropyl methacrylate, hydroxyhexyl acrylate, hydroxypropyl methacrylate, hydroxyhexyl acrylate, hydroxypropy
  • the monomer Mon3, if present at all, is preferably methyl acrylate.
  • the poly (meth) acrylate of the outer pressure-sensitive adhesive layer on a monomer composition is particularly preferred
  • the poly (meth) acrylate of the outer pressure-sensitive adhesive layer is composed of a monomer composition
  • the poly (meth) acrylates of the outer pressure-sensitive adhesive layer are preferably crosslinked thermally, in particular covalently and / or coordinatively.
  • Preferred covalent crosslinking agents are epoxy compounds, preferred coordinative crosslinking agents are aluminum chelates.
  • the weight-average molecular weight M w of the poly (meth) acrylates of the outer pressure-sensitive adhesive layer is preferably from 20,000 to 2,000,000 g / mol, particularly preferably from 100,000 to 1,500,000 g / mol, in particular from 200,000 to 1,200,000 g / mol.
  • the information on the average molecular weight M w in this document relates to the determination by gel permeation chromatography (see experimental section).
  • Outer thermoplastic film means that the thermoplastic film faces outwards and thus completes the structure of the adhesive tape on its side.
  • thermoplastic film has little or no adhesive properties, so that in every conceivable structure of the adhesive tape according to the invention, which comprises an outer thermoplastic film, it closes the side with the weaker bond strength. If the adhesive tape thus comprises an outer thermoplastic film, it has a lower bond strength on its side equipped with the outer thermoplastic film than on the opposite side, or it has no bond strength on its side equipped with the outer thermoplastic film.
  • the thermoplastic film preferably comprises at least one polymer selected from the group consisting of thermoplastic polyolefins (TPE-E or TPO), in particular thermoplastic polyolefin elastomers (POE) and thermoplastic polyolefin plastomers (POP); thermoplastic polystyrene elastomers (TPE-S or TPS), in particular styrene block copolymers (SBC); thermoplastic polyurethane elastomers (TPE-U or TPU); thermoplastic polyester elastomers and copolyesters (TPE-E or TPC); thermoplastic copolyamides (TPE-A or TPA); and thermoplastic vulcanizates as well as cross-linked thermoplastic polyolefin elastomers (TPE-V or TPV).
  • TPE-E or TPO thermoplastic polyolefins
  • POE thermoplastic polyolefin elastomers
  • POP thermoplastic polyolefin plastomers
  • thermoplastic film consists of at least one, particularly preferably one, polymer selected from the group consisting of thermoplastic polyolefins (TPE-E or TPO), in particular thermoplastic polyolefin elastomers (POE) and thermoplastic polyolefin elastomers (POP); thermoplastic polystyrene elastomers (TPE-S or TPS), in particular styrene block copolymers (SBC); thermoplastic polyurethane elastomers (TPE-U or TPU); thermoplastic polyester elastomers and copolyesters (TPE-E or TPC); thermoplastic copolyamides (TPE-A or TPA); and thermoplastic vulcanizates as well as cross-linked thermoplastic polyolefin elastomers (TPE-V or TPV).
  • TPE-E or TPO thermoplastic polyolefins
  • POE thermoplastic polyolefin elastomers
  • POP thermoplastic polyolefin
  • the structure or the layer sequence of an adhesive tape according to the invention comprises several variants.
  • the structure of the adhesive tape of the invention is limited to the polymer foam layer and an outer pressure-sensitive adhesive layer.
  • the adhesive tape of the invention thus consists of a) a polymer foam layer and b) an outer pressure-sensitive adhesive layer.
  • the polymer foam layer preferably corresponds to a polymer foam layer of embodiment II described there; the polymer foam layer, in particular the matrix material of the polymer foam layer, therefore preferably contains at least one poly (meth) acrylate. All the more detailed configurations described in the context of embodiment II of the polymer foam layer apply here accordingly.
  • the invention also comprises an embodiment in which an outer pressure-sensitive adhesive layer is arranged on each side of the polymer foam layer.
  • an outer pressure-sensitive adhesive layer is arranged on each side of the polymer foam layer.
  • the two outer pressure-sensitive adhesive layers are not identical in this case and differ in particular with regard to their bond strength.
  • the adhesive tape of the invention consists of a) a polymer foam layer and b) an outer thermoplastic film.
  • the polymer foam layer preferably corresponds to a polymer foam layer of embodiment III described there; the The polymer foam layer, in particular the matrix material of the polymer foam layer, therefore preferably contains at least one vinyl aromatic block copolymer. All the more detailed configurations described in the context of embodiment III of the polymer foam layer apply here accordingly.
  • the polymer foam layer is in particular sufficiently (adhesive) tacky to enable a sufficiently strong layer bond between itself and the outer thermoplastic film.
  • the adhesive tape consists of a) a polymer foam layer; b1) an outer pressure-sensitive adhesive layer on one side of the polymer foam layer and b2) an outer thermoplastic film on the side of the polymer foam layer opposite the outer pressure-sensitive adhesive layer.
  • the polymer foam layer preferably corresponds to a polymer foam layer of embodiment II described there; the polymer foam layer, in particular the matrix material of the polymer foam layer, therefore preferably contains at least one poly (meth) acrylate. All the more detailed configurations described in the context of embodiment II of the polymer foam layer apply here accordingly.
  • the polymer foam layer is in particular sufficiently (adhesive) tacky to enable a sufficiently strong layer bond between itself and the outer thermoplastic film.
  • the adhesive tape comprises, in addition to the polymer foam layer b1), an outer pressure-sensitive adhesive layer on one side of the polymer foam layer; b2) an outer thermoplastic film on the side of the polymer foam layer opposite the outer pressure-sensitive adhesive layer; and c) a further pressure-sensitive adhesive layer on the side of the polymer foam layer opposite the outer pressure-sensitive adhesive layer.
  • the further pressure-sensitive adhesive layer is thus located between the polymer foam layer and the outer thermoplastic film; it preferably connects the polymer foam layer with the outer thermoplastic film.
  • the statements made in relation to the outer pressure-sensitive adhesive layer apply to the further pressure-sensitive adhesive layer.
  • the further pressure-sensitive adhesive layer and the the outer pressure-sensitive adhesive layer is identical in terms of its composition; in particular, they are identical both in terms of their composition and in terms of their layer thickness.
  • the polymer foam layer preferably corresponds to a polymer foam layer of embodiment II described there; the polymer foam layer, in particular the matrix material of the polymer foam layer, therefore preferably contains at least one poly (meth) acrylate. All the more detailed configurations described in the context of embodiment II of the polymer foam layer apply here accordingly.
  • Another object of the invention is the use of an adhesive tape according to the invention for sealing a connection between two components.
  • the adhesive tape according to the invention advantageously allows rapid gluing and thus rapid production of the seal without slipping and without the need for curing. Waterproof and less susceptible to corrosion seals can be provided.
  • a simplified dismantling of the connection is possible, in that the component connected to the weaker adhesive side can be easily removed.
  • connection between the two components is initially effected in a different manner than by gluing; the connection between the components is particularly preferably a mechanical connection, for example a screw connection.
  • the two components are basically arbitrary, the term “components” is understood in a very broad sense.
  • the two components are preferably the housing and the cover of a vehicle battery; particularly preferably, when such a connection is sealed, the weaker adhesive side of the adhesive tape faces the cover.
  • the components can also belong to an electronic device, e.g. a smartphone or the like.
  • the adhesive tape according to the invention is likewise preferably pulled off a cross-wound reel within the scope of the use according to the invention; in particular, this step is automated.
  • the details of the molecular weight in this document relate to the determination by gel permeation chromatography. The determination is carried out on 100 ml clear-filtered sample (sample concentration 4 g / l). Tetrahydrofuran with 0.1% by volume of trifluoroacetic acid is used as the eluent. The measurement takes place at 25 ° C. A column type PSS-SDV, 5 m, 10 3 ⁇ , ID 8.0 mm 50 mm is used as the guard column.
  • the columns of the type PSS-SDV, 5 m, 10 3 ⁇ as well as 10 5 ⁇ and 10 6 ⁇ , each with ID 8.0 mm x 300 mm, are used (columns from Polymer Standards Service; detection using a Shodex RI71 differential refractometer) .
  • the flow rate is 1.0 ml per minute.
  • the calibration is carried out against PMMA standards (polymethyl methacrylate calibration).
  • 5 mm narrow strips were cut out of the adhesive tape to be examined and stuck onto a square metal plate (external dimensions 80 mm ⁇ 80 mm ⁇ 5 mm).
  • the strips were arranged in such a way that they form a closed square contour.
  • the ends of one strip were each connected flush with the side surface of the next end of the strip.
  • a paste (KMn0) was then applied to the inside of the square, which turns a distinct purple color on contact with water.
  • An identical metal plate was then placed on the structure and screwed. The screws were outside the square of strips of tape. The distance between the metal plates was set to exactly 2 mm by means of 2 pieces of 1 mm thick shim washers. This setup ensured that the water-reactive paste is in a closed space within the adhesive tape strips. A penetration of water would be recognizable by a discoloration and indicate a leak in the adhesive tape.
  • Re-detachability of the bonded substrate (simulation of the re-detachment of a bonded battery cover; reopenability):
  • the adhesive tape was applied with the more strongly adhesive side to an aluminum plate (450 ⁇ 250 mm, 2.5 mm thick) at a distance of 30 mm from the edge of the plate once all the way around.
  • Another aluminum plate (450 x 250 mm, 1 mm thick) with identical dimensions was attached to the free side (from above). 2 mm thick shims were inserted into the joints on each side, then the composite was pressed together in a screw clamp. The aluminum plates were then screwed together using holes in the corners of the plates for this purpose.
  • the composite formed in this way was stored for 10 days in a climatic chamber at 40 ° C. and 100% relative humidity. After removal, it was reconditioned for 24 hours at 23 ° C. and 50% relative humidity.
  • a - tesa ® 61102 (closed-cell EPDM rubber foam, coated on one side with an acrylate adhesive, total thickness 3,200 ⁇ m; tesa)
  • Foam tape coated on both sides with acrylate pressure-sensitive adhesive, total thickness 2,900 gm; tesa), laminated on one side with a thermoplastic polyurethane film (Platilon ® U04 / PE, 30 gm; Bayer)

Abstract

The invention relates to a sealing element with high sealing effect against air and moisture, which is easy to apply, and which moreover offers the possibility to reopen the sealed gap in an uncomplicated manner. Said solution is provided by an adhesive tape with differing adhesive power on the two main sides, which comprises a) a polymer foam layer and b) an outer adhesive compound layer and/or an outer thermoplastic film on one side of the polymer foam layer and is characterized in that, where the adhesive tape comprises an outer adhesive compound layer, the tape has a greater adhesive power on the side provided with the outer adhesive compound layer than on the opposing side and/or, where the adhesive tape comprises an outer thermoplastic film, the tape has a lower adhesive power on the side provided with the outer thermoplastic film than on the opposing side. The invention furthermore relates to the use of an adhesive tape according to the invention for sealing a joint between two components.

Description

Beschreibung description
Einseitig schwach oder nicht klebendes Abdichtungsband Sealing tape weakly or non-adhesive on one side
Die Erfindung betrifft das technische Gebiet der Klebebänder, wie sie im Haushalt und in der Industrie vielfach zum Verbinden zweier Substrate, aber auch zu anderen Zwecken wie beispielsweise zum Schutz von Oberflächen oder zum Abdichten eingesetzt werden. Spezifischer wird ein zum Abdichten geeignetes Schaum-Klebeband vorgeschlagen, das an seinen beiden Hauptseiten unterschiedliche Klebkräfte aufweist oder nur an einer seiner beiden Hauptseiten haftklebend ausgestattet ist. The invention relates to the technical field of adhesive tapes, as they are often used in households and in industry for joining two substrates, but also for other purposes such as protecting surfaces or for sealing. More specifically, a foam adhesive tape suitable for sealing is proposed which has different adhesive strengths on its two main sides or is provided with pressure-sensitive adhesive on only one of its two main sides.
Für viele Konstruktionen auf unterschiedlichen Gebieten der Technik, beispielsweise im Bauwesen und im Fahrzeugbau, werden Abdichtungen benötigt. Die dafür verwendeten Dichtelemente sollen Spalte, wie sie beim Verbinden zweier Bauteile nahezu unvermeidlich entstehen, häufig gegen das Eindringen von Feuchtigkeit und Luft abdichten, um dahinter liegende Teile vor dadurch hervorgerufenen Schäden, z.B. vor Korrosion, zu bewahren. Mechanische Verbindungen, wie sie z.B. durch Schrauben bewirkt werden, sind in aller Regel nicht in der Lage, eine ausreichende Abdichtung zu bewirken. Seals are required for many constructions in different fields of technology, for example in construction and in vehicle construction. The sealing elements used for this purpose should often seal gaps, which are almost inevitable when connecting two components, against the ingress of moisture and air, in order to protect the parts behind them from damage caused by this, e.g. from corrosion. Mechanical connections, such as those made by screws, are usually not able to produce a sufficient seal.
Häufig werden daher z.B. Silikon-Dichtmassen verwendet, um eine entsprechende Versiegelung der hergestellten Verbindungen zu erreichen. Derartige Dichtmassen lassen sich recht zuverlässig verarbeiten, benötigen jedoch eine bestimmte Zeit zum Aushärten und verursachen damit häufig prozesstechnische Schwierigkeiten. Ähnlich verhält es sich mit anderen strukturellen Kleb- bzw. Dichtstoffen, z.B. mit solchen auf Basis von Epoxiden oder Polyurethanen. For this reason, silicone sealants, for example, are often used in order to achieve a suitable seal for the connections made. Such sealing compounds can be processed quite reliably, but require a certain time to harden and thus often cause process engineering difficulties. The situation is similar with other structural adhesives or sealants, e.g. those based on epoxides or polyurethanes.
Auch Silikonschäume werden als Dichtmassen eingesetzt, sie zeichnen sich durch gute Flammschutzeigenschaften und ihre Wiederverwendbarkeit aus. Andererseits ist es schwierig, sie in einem automatisierten Prozess zu verarbeiten, zudem sind sie vergleichsweise teuer. Butyl-Dichtmassen sind etabliert und preiswert, andererseits hinsichtlich ihrer Dosierung schwierig zu kontrollieren und wenig alterungsbeständig. Zudem werden sie bei höheren Drücken häufig aus dem Spalt gequetscht. Silicone foams are also used as sealing compounds; they are characterized by good flame retardant properties and their reusability. On the other hand, it is difficult to process them in an automated process, and they are also comparatively expensive. Butyl sealing compounds are established and inexpensive, on the other hand difficult to control with regard to their dosage and not very resistant to aging. In addition, they are often squeezed out of the gap at higher pressures.
Elastische Dichtstoffe wie Gummis bzw. Styrol-Butadien-Kautschuke bieten bewährte Abdichtungseigenschaften und sind zudem sehr temperaturstabil. Da sie nicht selbsthaftend sind, ist ihre Handhabung allerdings eher schwierig; zudem sind sie unflexibel, das jeweilige Dichtelement muss daher exakt zum abzudichtenden Spalt passen. Elastic sealants such as rubbers or styrene-butadiene rubbers offer proven sealing properties and are also very temperature-stable. Since they are not self-adhesive, however, their handling is rather difficult; In addition, they are inflexible, so the respective sealing element must fit exactly to the gap to be sealed.
Polyurethanschäume zeigen ein gutes Kompressionsverhalten und lassen sich automatisiert verarbeiten; zudem sind sogenannte foam-/n-p/ace-Anwendungen möglich. Nachteilig sind Schwankungen in den Abmessungen des betreffenden Schaums, zudem sind diese Stoffe anfällig für Korrosion und Abbau unter dem Einfluss bestimmter Reinigungsmittel. Polyurethane foams show good compression behavior and can be processed automatically; so-called foam / n-p / ace applications are also possible. Fluctuations in the dimensions of the foam in question are disadvantageous, and these substances are also susceptible to corrosion and degradation under the influence of certain cleaning agents.
Ein ähnliches Eigenschaftsprofil zeigen EPDM-Schäume; auch mit ihnen lässt sich wegen ihrer unregelmäßigen Oberflächengestaltung nur eine begrenzte Abdichtungswirkung erzielen. EPDM foams show a similar profile of properties; Even with them, only a limited sealing effect can be achieved because of their irregular surface design.
WO 2009/086056 A2 beschreibt demgegenüber ein sogenanntes flashing tape, das in konstruktiven Anwendungen einen Feuchtigkeitsausschluss bewirken soll. Der offenbarte Aufbau des Tapes umfasst eine viskoelastische Kernschicht und mindestens eine elastomere Außenschicht; darüber hinaus kann eine Haftklebmasseschicht umfasst sein, um das Tape an ein Substrat zu kleben. In contrast, WO 2009/086056 A2 describes what is known as a flashing tape, which is intended to exclude moisture in structural applications. The disclosed structure of the tape comprises a viscoelastic core layer and at least one elastomeric outer layer; In addition, a pressure-sensitive adhesive layer can be included in order to adhere the tape to a substrate.
Es besteht ein anhaltender Bedarf an gut anwendbaren Systemen zur Abdichtung von Verbindungen zwischen zwei Bauteilen. Aufgabe der Erfindung war es somit, ein einfach zu applizierendes Dichtelement mit hoher Abdichtungswirkung gegen Luft und Feuchtigkeit zur Verfügung zu stellen, das zudem die Möglichkeit bietet, den abgedichteten Spalt unkompliziert wieder zu öffnen. There is a continuing need for well applicable systems for sealing connections between two components. The object of the invention was therefore to provide a sealing element which is easy to apply and has a high sealing effect against air and moisture and which also offers the possibility of uncomplicated reopening of the sealed gap.
Ein erster und allgemeiner Gegenstand der Erfindung, mit dem diese Aufgabe gelöst wird, ist ein Klebeband mit unterschiedlicher Klebkraft auf beiden Hauptseiten, das a) eine Polymerschaumschicht und b) eine äußere Haftklebmasseschicht und/oder eine äußere thermoplastische Folie auf jeweils einer Seite der Polymerschaumschicht; umfasst und dadurch gekennzeichnet ist, dass, sofern das Klebeband eine äußere Haftklebmasseschicht umfasst, es auf seiner mit der äußeren Haftklebmasseschicht ausgestatteten Seite eine höhere Klebkraft aufweist als auf der gegenüberliegenden Seite und/oder, sofern das Klebeband eine äußere thermoplastische Folie umfasst, es auf seiner mit der äußeren thermoplastischen Folie ausgestatteten Seite eine niedrigere Klebkraft aufweist als auf der gegenüberliegenden Seite. A first and general object of the invention, with which this object is achieved, is an adhesive tape with different adhesive strength on both main sides, which has a) a polymer foam layer and b) an outer pressure-sensitive adhesive layer and / or an outer thermoplastic film on each side of the polymer foam layer; and is characterized in that, if the adhesive tape comprises an outer pressure-sensitive adhesive layer, it has a higher bond strength on its side equipped with the outer pressure-sensitive adhesive layer than on the opposite side and / or, if the adhesive tape comprises an outer thermoplastic film, it has a lower bond strength on its side equipped with the outer thermoplastic film than on the opposite side.
Wie sich gezeigt hat, lässt sich ein solches Klebeband vorteilhaft zum Abdichten von Verbindungen zwischen Bauteilen verwenden, wobei es zum einen eine einfache, sichere und exakte Applikation erlaubt und zum anderen eine einfache Demontage der Verbindung ermöglicht. Zudem lässt es sich gut automatisiert verarbeiten und zeigt ein kontrolliertes Kompressionsverhalten. As has been shown, such an adhesive tape can advantageously be used to seal connections between components, on the one hand allowing simple, safe and precise application and on the other hand enabling simple dismantling of the connection. In addition, it can be processed automatically and shows a controlled compression behavior.
Der allgemeine Ausdruck „Klebeband“ umfasst im Sinne dieser Erfindung alle ein- oder beidseitig selbstklebend ausgestatteten flächigen Gebilde wie in zwei Dimensionen ausgedehnte Folien oder Folienabschnitte, Bänder mit ausgedehnter Länge und begrenzter Breite, Bandabschnitte, Etiketten, Stanzlinge und dergleichen sowie entsprechende Mehrschichtanordnungen. The general expression “adhesive tape” in the context of this invention includes all flat structures with one or both sides self-adhesive, such as films or film sections extended in two dimensions, tapes with extended length and limited width, tape sections, labels, diecuts and the like as well as corresponding multilayer arrangements.
Häufig sind Klebebänder bzw. deren Klebmassen mit einem sogenannten Releaseliner abgedeckt bzw. geschützt, der vor der Applikation des Klebebandes entfernt wird. Ein Releaseliner ist nicht Bestandteil des Klebebands, sondern nur ein Hilfsmittel zu dessen Herstellung und/oder Lagerung. Often adhesive tapes or their adhesives are covered or protected with what is known as a release liner, which is removed before the adhesive tape is applied. A release liner is not part of the adhesive tape, but only an aid for its production and / or storage.
Üblicherweise werden Klebebänder Usually adhesive tapes are used
- in festen Längen wie zum Beispiel als Meterware oder - in fixed lengths such as by the meter or
- als Endlosware in Form von Rollen (archimedische Spirale) oder auf einen Kern gewickelten Spulen zur Verfügung gestellt. - made available as continuous goods in the form of rolls (Archimedean spiral) or coils wound on a core.
Polvmerschaumschicht Polverschaumschicht
Das erfindungsgemäße Klebeband umfasst eine Polymerschaumschicht. Unter einer „Polymerschaumschicht“ bzw. einem „Polymerschaum“ wird ein Werkstoff mit über seine ganze Masse verteilten offenen und/oder geschlossenen Zellen verstanden, der eine Rohdichte aufweist, die niedriger ist als die der polymeren Gerüstsubstanz. Der Ausdruck „Schaum“ bedeutet insbesondere, dass die betreffende Schicht Gebilde aus gasgefüllten, häufig kugel- oder polyederförmigen Zellen umfasst, welche durch flüssige, halbflüssige, höherviskose oder feste Zellstege oder ein eigenes Hüllenmaterial begrenzt werden und welche in einem solchen Anteil in der betreffenden Schicht vorliegen, dass die Dichte der geschäumten Schicht gegenüber der Dichte des Matrixmaterials, also der Gesamtheit der nicht gasförmigen Materialien außer eventuell vorhandenem eigenen Hüllenmaterial der Schaumzellen, verringert ist. The adhesive tape according to the invention comprises a polymer foam layer. A “polymer foam layer” or a “polymer foam” is understood to mean a material with open and / or closed cells distributed over its entire mass, which has a bulk density that is lower than that of the polymeric framework. The term "foam" means in particular that the layer in question comprises structures of gas-filled, often spherical or polyhedral cells, which are delimited by liquid, semi-liquid, high viscosity or solid cell webs or their own shell material and which are in such a proportion in the layer in question present that the density of the foamed layer compared to the density of the matrix material, that is to say the entirety of the non-gaseous materials except for any own shell material of the foam cells that may be present.
Bei der Gerüstsubstanz, im Folgenden auch als Polymerschaummatrix, Schaummatrix, Matrix oder Matrixmaterial bezeichnet, handelt es sich erfindungsgemäß um ein oder mehrere Polymere, die mit Zuschlagstoffen abgemischt sein können. Unter „offenen Zellen“ werden Hohlräume innerhalb des Schaums verstanden, die nicht vollständig von Gerüstsubstanz oder einem eigenen Hüllenmaterial umgeben sind. Unter „geschlossenen Zellen“ werden Hohlräume verstanden, die vollständig von Gerüstsubstanz oder einem eigenen Hüllenmaterial umgeben sind. Die Polymerschaumschicht des erfindungsgemäßen Klebebands ist bevorzugt ein geschlossenzelliger Schaum. The framework substance, also referred to below as polymer foam matrix, foam matrix, matrix or matrix material, is, according to the invention, one or more polymers which can be mixed with additives. “Open cells” are hollow spaces within the foam that are not completely surrounded by structural substance or a separate shell material. “Closed cells” are understood to mean cavities that are completely surrounded by structural substance or a separate shell material. The polymer foam layer of the adhesive tape according to the invention is preferably a closed-cell foam.
Allgemein bevorzugt enthält die Polymerschaumschicht, insbesondere das Matrixmaterial der Polymerschaumschicht, zu mindestens 35 Gew.-%, stärker bevorzugt zu mindestens 50 Gew.- % und besonders bevorzugt zu mindestens 70 Gew.-%, insbesondere zu mindestens 80 Gew.- %, beispielsweise zu mindestens 90 Gew.-%, jeweils bezogen auf das Gesamtgewicht der Polymerschaumschicht bzw. das Gesamtgewicht des Matrixmaterials, ein oder mehrere Polymere. Dieser Polymergehalt kann je nach Art des Basispolymers variieren. Mögliche Polymere der Polymerschaumschicht umfassen Polyolefine, z.B. Polyethylene wie high density Polyethylen (HDPE), low density Polyethylen (LDPE), linear low density Polyethylen (LLDPE) und linear ultra low density Polyethylen, Polypropylen und Polybutylen; Vinyl- Copolymere, z.B. Polyvinylchlorid und Polyvinylacetat; olefinische Random- oder Block- Copolymere, z.B. Ethylen-Methylacrylat-Copolymere, Ethylen-Vinylacetat-Copolymere und Ethylen-Propylen-Copolymere sowie Ethylen-Propylen-Dien-Terpolymere (EPDM), ferner Polyalkylene, die aus Monomergemischen hergestellt werden, welche 1 ) ein erstes Alken ausgewählt aus Ethylen, Propylen oder einem Gemisch davon, und 2) ein zweites Alken ausgewählt aus 1 ,2-Alkenen mit 4 bis 8 Kohlenstoffatomen wie 1 ,2-Buten, 1 ,2-Hexen oder 1 ,2- Octen umfassen; Acrylnitril-Butadien-Styrol-Copolymere; Acrylpolymere und -Copolymere; Polycarbonate; Polyimide; Polyurethane, beispielsweise thermoplastische Polyurethane, insbesondere Polyester-basierte thermoplastische Polyurethane; Polyester, z.B. Polyethylenterephthalat; sowie Kombinationen und Blends der vorgenannten Polymere. Beispielhafte Blends umfassen Polypropylen-Polyethylen-Blends, PVC-Nitrilkautschuk- Blends, Polyurethan-Polyolefin-Blends, Polyurethan-Polycarbonat-Blends und Polyurethan- Polyester-Blends. Ferner können Blends thermoplastischer Polymere, elastomerer Polymere und Kombinationen davon umfasst sein. Weitere Blends können Styrol-Butadien-Copolymere, Polychloroprene, z.B. Neopren, Nitrilkautschuke, Butylkautschuke, Polysulfidkautschuke, cis- 1 ,4-Polyisopren, Ethylen-Propylen-Terpolymere, z.B. EPDM-Kautschuk, Silikonkautschuke, Silikon-Polyharnstoff-Blockcopolymere, Polyurethankautschuke, Naturkautschuke,Generally preferably, the polymer foam layer, in particular the matrix material of the polymer foam layer, contains at least 35% by weight, more preferably at least 50% by weight and particularly preferably at least 70% by weight, in particular at least 80% by weight, for example at least 90% by weight, based in each case on the total weight of the polymer foam layer or the total weight of the matrix material, of one or more polymers. This polymer content can vary depending on the type of base polymer. Possible polymers of the polymer foam layer include polyolefins, for example polyethylenes such as high density polyethylene (HDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE) and linear ultra low density polyethylene, polypropylene and polybutylene; Vinyl copolymers such as polyvinyl chloride and polyvinyl acetate; olefinic random or block copolymers, e.g. ethylene-methyl acrylate copolymers, ethylene-vinyl acetate copolymers and ethylene-propylene copolymers as well as ethylene-propylene-diene terpolymers (EPDM), also polyalkylenes, which are produced from monomer mixtures, which 1) a first alkene selected from ethylene, propylene or a mixture thereof, and 2) a second alkene selected from 1,2-alkenes having 4 to 8 carbon atoms such as 1,2-butene, 1,2-hexene or 1,2-octene ; Acrylonitrile-butadiene-styrene copolymers; Acrylic polymers and copolymers; Polycarbonates; Polyimides; Polyurethanes, for example thermoplastic polyurethanes, in particular polyester-based thermoplastic polyurethanes; Polyesters, for example polyethylene terephthalate; as well as combinations and blends of the aforementioned polymers. Exemplary blends include polypropylene-polyethylene blends, PVC-nitrile rubber blends, polyurethane-polyolefin blends, polyurethane-polycarbonate blends and polyurethane-polyester blends. Furthermore, blends of thermoplastic polymers, elastomeric polymers and combinations thereof can be included. Further blends can be styrene-butadiene copolymers, polychloroprene, e.g. neoprene, nitrile rubbers, butyl rubbers, polysulfide rubbers, cis-1,4-polyisoprene, ethylene-propylene terpolymers, e.g. EPDM rubber, silicone rubbers, Silicone-polyurea block copolymers, polyurethane rubbers, natural rubbers,
Acrylatkautschuke, thermoplastische Kautschuke, z.B. Styrol-Butadien-Blockcopolymere, Styrol-Isopren-Styrol-Blockcopolymere, Styrol-Ethylen/Butylen-Styrol-Blockcopolymere,Acrylate rubbers, thermoplastic rubbers, e.g. styrene-butadiene block copolymers, styrene-isoprene-styrene block copolymers, styrene-ethylene / butylene-styrene block copolymers,
Styrol-Ethylen/Propylen-Styrol-Blockcopolymere, thermoplastische Polyolefinkautschuke und Kombinationen davon umfassen. Styrene-ethylene / propylene-styrene block copolymers, thermoplastic polyolefin rubbers, and combinations thereof.
Das Polymer bzw. die Polymere der Polymerschaumschicht, insbesondere des Matrixmaterials der Polymerschaumschicht, sind bevorzugt ausgewählt aus der Gruppe bestehend aus Polyolefinen; Polyurethanen; Polyvinylchlorid (PVC); Blends aus PVC und Nitrilkautschuk; Terpolymerisaten aus Ethylen, Propylen und einem nicht konjugierten Dien (EPDM); Copolymeren aus Ethylen und einem mit einer polaren Gruppe substituierten Ethylen; Blends aus Polyethylen und einem Polymer aus einem mit einer polaren Gruppe substituierten Ethylen; Poly(meth)acrylaten; Blends aus Poly(meth)acrylat und Synthesekautschuk sowie Gemischen aus zwei oder mehreren der vorstehend genannten Polymere. Die Polymerschaumschicht, insbesondere das Matrixmaterial der Polymerschaumschicht, enthält somit bevorzugt zu mindestens 35 Gew.-%, stärker bevorzugt zu mindestens 50 Gew.-% und besonders bevorzugt zu mindestens 70 Gew.-%, insbesondere zu mindestens 80 Gew.-%, beispielsweise zu mindestens 90 Gew.-%, jeweils bezogen auf das Gesamtgewicht der Polymerschaumschicht bzw. das Gesamtgewicht des Matrixmaterials, ein oder mehrere Polymere ausgewählt aus der Gruppe bestehend aus Polyolefinen; Polyurethanen; Polyvinylchlorid (PVC); Blends aus PVC und Nitrilkautschuk; Terpolymerisaten aus Ethylen, Propylen und einem nicht konjugierten Dien (EPDM); Copolymeren aus Ethylen und einem mit einer polaren Gruppe substituierten Ethylen; Blends aus Polyethylen und einem Polymer aus einem mit einer polaren Gruppe substituierten Ethylen; Poly(meth)acrylaten; Blends aus Poly(meth)acrylat und Synthesekautschuk sowie Gemischen aus zwei oder mehreren der vorstehend genannten Polymere. Besonders bevorzugt enthält das Matrixmaterial der Polymerschaumschicht keine weiteren Polymere außer einem oder mehreren Polymeren ausgewählt aus der Gruppe bestehend aus Polyolefinen; Polyurethanen; Polyvinylchlorid (PVC); Blends aus PVC und Nitrilkautschuk; Terpolymerisaten aus Ethylen, Propylen und einem nicht konjugierten Dien (EPDM); Copolymeren aus Ethylen und einem mit einer polaren Gruppe substituierten Ethylen; Blends aus Polyethylen und einem Polymer aus einem mit einer polaren Gruppe substituierten Ethylen; Poly(meth)acrylaten; Blends aus Poly(meth)acrylat und Synthesekautschuk sowie Gemischen aus zwei oder mehreren der vorstehend genannten Polymere. The polymer or polymers of the polymer foam layer, in particular the matrix material of the polymer foam layer, are preferably selected from the group consisting of polyolefins; Polyurethanes; Polyvinyl chloride (PVC); Blends of PVC and nitrile rubber; Terpolymers of ethylene, propylene and a non-conjugated diene (EPDM); Copolymers of ethylene and an ethylene substituted with a polar group; Blends of polyethylene and a polymer of an ethylene substituted with a polar group; Poly (meth) acrylates; Blends of poly (meth) acrylate and synthetic rubber and mixtures of two or more of the aforementioned polymers. The polymer foam layer, in particular the matrix material of the polymer foam layer, thus preferably contains at least 35% by weight, more preferably at least 50% by weight and particularly preferably at least 70% by weight, in particular at least 80% by weight, for example at least 90% by weight, based in each case on the total weight of the polymer foam layer or the total weight of the matrix material, one or more polymers selected from the group consisting of polyolefins; Polyurethanes; Polyvinyl chloride (PVC); Blends of PVC and nitrile rubber; Terpolymers of ethylene, propylene and a non-conjugated diene (EPDM); Copolymers of ethylene and an ethylene substituted with a polar group; Blends of polyethylene and a polymer of an ethylene substituted with a polar group; Poly (meth) acrylates; Blends of poly (meth) acrylate and synthetic rubber and mixtures of two or more of the aforementioned polymers. The matrix material of the polymer foam layer particularly preferably contains no further polymers apart from one or more polymers selected from the group consisting of polyolefins; Polyurethanes; Polyvinyl chloride (PVC); Blends of PVC and nitrile rubber; Terpolymers of ethylene, propylene and a non-conjugated diene (EPDM); Copolymers of ethylene and an ethylene substituted with a polar group; Blends of polyethylene and a polymer of an ethylene substituted with a polar group; Poly (meth) acrylates; Blends of poly (meth) acrylate and synthetic rubber and mixtures of two or more of the aforementioned polymers.
Unter einem „Polyolefin“ wird ein Polymer der allgemeinen Struktur A “polyolefin” is a polymer of general structure
-[CH2-CRiR2-]n- verstanden, worin Ri und R2 unabhängig voneinander ein Wasserstoffatom oder eine lineare oder verzweigte gesättigte aliphatische oder cycloaliphatische Gruppe bezeichnen. Das Polyolefin ist bevorzugt Polyethylen, Polypropylen, Polybutylen oder ein Gemisch aus diesen. Das Polyethylen kann dabei einen oder mehrere der an sich bekannten Polyethylen-Typen wie HDPE, LDPE, LLDPE, VLDPE, VLLDPE, MDPE (medium-density PE), metallocene PE-Typen wie mLLDPE und mHDPE, Blends aus diesen Polyethylen-Typen und Gemische davon umfassen. Das Polypropylen ist bevorzugt ein kristallines Polypropylen, stärker bevorzugt ein Homopolypropylen (hPP). In einer speziellen Ausführungsform I der Polymerschaumschicht enthält das Matrixmaterial der Polymerschaumschicht keine weiteren Polymere außer einem oder mehreren Polyolefinen. - [CH2-CRiR2-] n- understood, in which Ri and R2 independently of one another are a hydrogen atom or a linear or branched saturated aliphatic or cycloaliphatic group describe. The polyolefin is preferably polyethylene, polypropylene, polybutylene or a mixture of these. The polyethylene can be one or more of the polyethylene types known per se, such as HDPE, LDPE, LLDPE, VLDPE, VLLDPE, MDPE (medium-density PE), metallocene PE types such as mLLDPE and mHDPE, blends of these types of polyethylene and mixtures of which include. The polypropylene is preferably a crystalline polypropylene, more preferably a homopolypropylene (hPP). In a special embodiment I of the polymer foam layer, the matrix material of the polymer foam layer does not contain any further polymers apart from one or more polyolefins.
Unter einem Copolymer aus Ethylen und einem mit einer polaren Gruppe substituierten Ethylen wird ein Polymer der allgemeinen Struktur -[CH2-CR3R4 -]n- verstanden, worin R3 oder R4 ein Wasserstoffatom bezeichnen und der jeweils verbleibende Substituent eine mindestens ein Sauerstoffatom enthaltende Gruppe bezeichnet. Bevorzugt ist das Copolymer aus Ethylen und einem mit einer polaren Gruppe substituierten Ethylen ein Ethylen-Vinylacetat-Copolymer (EVA), ein Ethylen-Methylacrylat-Copolymer (EMA), ein Ethylen-Ethylacrylat-Copolymer (EEA), ein Ethylen-Acrylsäure-Copolymer (EAA), ein Ethylen-Butylacrylat-Copolymer (EBA) oder ein Gemisch aus diesen. Das EVA hat bevorzugt einen Vinylacetat-Gehalt von 1 bis 70 Gew.-%, stärker bevorzugt von 3 bis 30 Gew.-%, insbesondere von 5 bis 20 Gew.-%. In einer spezielleren Variante der Ausführungsform I der Polymerschaumschicht enthält das Matrixmaterial der Polymerschaumschicht keine weiteren Polymere außer einem oder mehreren Copolymeren aus Ethylen und einem mit einer polaren Gruppe substituierten Ethylen. Insbesondere ist dabei das Copolymer aus Ethylen und einem mit einer polaren Gruppe substituierten Ethylen ein Ethylen-Vinylacetat-Copolymer (EVA). Besonders bevorzugt enthält in dieser Ausführungsform daher das Matrixmaterial der Polymerschaumschicht mindestens ein Ethylen-Vinylacetat-Copolymer (EVA). Insbesondere beträgt der Anteil der Gesamtheit aller Ethylen-Vinylacetat-Copolymere an dem Matrixmaterial der Polymerschaumschicht mindestens 50 Gew.-%, stärker bevorzugt mindestens 70 Gew.-% und besonders bevorzugt mindestens 80 Gew.-%, insbesondere mindestens 85 Gew.-%, beispielsweise mindestens 90 Gew.-%, jeweils bezogen auf das Gesamtgewicht des Matrixmaterials. Ganz besonders bevorzugt enthält das Matrixmaterial keine weiteren Polymere außer einem oder mehreren Ethylen-Vinylacetat-Copolymeren (EVA). A copolymer of ethylene and an ethylene substituted by a polar group is understood to mean a polymer of the general structure - [CH2-CR3R4 -] n-, where R3 or R4 denote a hydrogen atom and the remaining substituent denotes a group containing at least one oxygen atom. The copolymer of ethylene and an ethylene substituted by a polar group is preferably an ethylene-vinyl acetate copolymer (EVA), an ethylene-methyl acrylate copolymer (EMA), an ethylene-ethyl acrylate copolymer (EEA), an ethylene-acrylic acid copolymer (EAA), an ethylene-butyl acrylate copolymer (EBA) or a mixture of these. The EVA preferably has a vinyl acetate content of 1 to 70% by weight, more preferably 3 to 30% by weight, in particular 5 to 20% by weight. In a more specific variant of embodiment I of the polymer foam layer, the matrix material of the polymer foam layer contains no further polymers apart from one or more copolymers of ethylene and an ethylene substituted by a polar group. In particular, the copolymer of ethylene and an ethylene substituted by a polar group is an ethylene-vinyl acetate copolymer (EVA). In this embodiment, the matrix material of the polymer foam layer particularly preferably contains at least one ethylene-vinyl acetate copolymer (EVA). In particular, the proportion of all ethylene-vinyl acetate copolymers in the matrix material of the polymer foam layer is at least 50% by weight, more preferably at least 70% by weight and particularly preferably at least 80% by weight, in particular at least 85% by weight, for example at least 90% by weight, based in each case on the total weight of the matrix material. The matrix material very particularly preferably contains no further polymers apart from one or more ethylene-vinyl acetate copolymers (EVA).
Bevorzugt ist das Matrixmaterial der Polymerschaumschicht vernetzt. Die Vernetzung findet bevorzugt vor der Schäumung des Matrixmaterials statt. Matrixmaterialien, die Polymere ausgewählt aus Polyolefinen und Copolymeren aus Ethylen und einem mit einer polaren Gruppe substituierten Ethylen enthalten, werden bevorzugt mit Elektronenstrahlen vernetzt. In Frage kommen auch chemische Vernetzungsmethoden, beispielsweise eine Vernetzung über aufgepfropfte Silan-Reste mit hydrolysierbaren Gruppen, welche dann unter dem Einfluss von Feuchtigkeit und Katalyse miteinander reagieren können; ferner eine Vernetzung über zugesetzte Silane, welche eine radikalisch polymerisierbare Doppelbindung enthalten und mit Radikalen, die in den Poylmerketten gebildet werden, abreagieren können; sowie eine Vernetzung über zugesetzte Peroxide, die ebenfalls mit Radikalen abreagieren. The matrix material of the polymer foam layer is preferably crosslinked. The crosslinking takes place preferably before the matrix material is foamed. Matrix materials which contain polymers selected from polyolefins and copolymers of ethylene and an ethylene substituted with a polar group are preferably crosslinked with electron beams. Chemical crosslinking methods are also possible, for example crosslinking via grafted silane residues with hydrolyzable groups, which are then influenced by Moisture and catalysis can react with one another; furthermore crosslinking via added silanes which contain a free-radically polymerizable double bond and can react with free radicals which are formed in the polymer chains; as well as crosslinking via added peroxides, which also react with radicals.
In einer Ausführungsform II der Polymerschaumschicht enthält die Polymerschaumschicht, insbesondere das Matrixmaterial der Polymerschaumschicht, mindestens ein Poly(meth)acrylat. Unter einem „Poly(meth)acrylat“ wird ein Polymer verstanden, welches durch radikalische Polymerisation von Acryl- und/oder Methacrylmonomeren sowie gegebenenfalls weiteren, copolymerisierbaren Monomeren erhältlich ist. Insbesondere wird unter einem „Poly(meth)acrylat“ ein Polymer verstanden, dessen Monomerbasis zu mindestens 50 Gew.-% aus Acrylsäure, Methacrylsäure, Acrylsäureestern und/oder Methacrylsäureestern besteht, wobei Acrylsäureester und/oder Methacrylsäureester zumindest anteilig, bevorzugt zu mindestens 30 Gew.-%, bezogen auf die gesamte Monomerbasis des betreffenden Polymers, enthalten sind. In one embodiment II of the polymer foam layer, the polymer foam layer, in particular the matrix material of the polymer foam layer, contains at least one poly (meth) acrylate. A “poly (meth) acrylate” is understood to mean a polymer which can be obtained by free-radical polymerization of acrylic and / or methacrylic monomers and optionally other copolymerizable monomers. In particular, a “poly (meth) acrylate” is understood to mean a polymer whose monomer base consists of at least 50% by weight of acrylic acid, methacrylic acid, acrylic acid esters and / or methacrylic acid esters, acrylic acid esters and / or methacrylic acid esters at least proportionally, preferably at least 30% by weight .-%, based on the total monomer base of the polymer in question, are included.
Bevorzugt enthält die Polymerschaumschicht Poly(meth)acrylate zu insgesamt 40 bis 99,9 Gew.-%, stärker bevorzugt zu insgesamt 60 bis 98 Gew.-%, insbesondere zu insgesamt 75 bis 95 Gew.-%, beispielsweise zu insgesamt 80 bis 90 Gew.-%, jeweils bezogen auf das Gesamtgewicht der Polymerschaumschicht. Es können ein (einziges) Poly(meth)acrylat oder mehrere Poly(meth)acrylate enthalten sein; der Pluralausdruck „Poly(meth)acrylate“ schließt also - auch im Fortgang der vorliegenden Beschreibung - in seiner Bedeutung ebenso wie der Ausdruck „insgesamt“ sowohl das Vorliegen eines einzigen Poly(meth)acrylats als auch das Vorliegen mehrerer Poly(meth)acrylate ein. The polymer foam layer preferably contains a total of 40 to 99.9% by weight of poly (meth) acrylates, more preferably a total of 60 to 98% by weight, in particular a total of 75 to 95% by weight, for example a total of 80 to 90% by weight % By weight, based in each case on the total weight of the polymer foam layer. It can contain a (single) poly (meth) acrylate or several poly (meth) acrylates; The plural term “poly (meth) acrylates” thus includes - also in the continuation of the present description - in its meaning as well as the expression “as a whole” both the presence of a single poly (meth) acrylate and the presence of several poly (meth) acrylates .
Die Glasübergangstemperatur der Poly(meth)acrylate beträgt bevorzugt < 0 °C, stärker bevorzugt zwischen -20 und -50 °C. Die Glasübergangstemperatur von Polymeren oder von Polymerblöcken in Blockcopolymeren wird erfindungsgemäß mittels Dynamischer Scanning Kalorimetrie (DSC) bestimmt. Dazu werden ca. 5 mg einer unbehandelten Polymerprobe in ein Aluminiumtiegelchen (Volumen 25 mI) eingewogen und mit einem gelochten Deckel verschlossen. Zur Messung wird ein DSC 204 F1 der Firma Netzsch verwendet. Es wird zwecks Inertisierung unter Stickstoff gearbeitet. Die Probe wird zunächst auf -150 °C abgekühlt, dann mit einer Heizrate von 10 K/min bis +150 °C aufgeheizt und erneut auf -150 °C abgekühlt. Die sich anschließende zweite Heizkurve wird erneut bei 10 K/min gefahren und die Änderung der Wärmekapazität aufgenommen. Glasübergänge werden als Stufen im Thermogramm erkannt. Bevorzugt enthält das Poly(meth)acrylat zumindest ein anteilig einpolymerisiertes funktionelles, besonders bevorzugt mit Epoxidgruppen unter Ausbildung einer kovalenten Bindung reaktives Monomer. Ganz besonders bevorzugt enthält das anteilig einpolymerisierte funktionelle, besonders bevorzugt mit Epoxidgruppen unter Ausbildung einer kovalenten Bindung reaktive Monomer mindestens eine funktionelle Gruppe ausgewählt aus der Gruppe bestehend aus Carbonsäuregruppen, Sulfonsäuregruppen, Phosphonsäuregruppen, Hydroxygruppen, Säureanhydridgruppen, Epoxidgruppen und Aminogruppen; insbesondere enthält es mindestens eine Carbonsäuregruppe. Äußerst bevorzugt enthält das Poly(meth)acrylat anteilig einpolymerisierte Acrylsäure und/oder Methacrylsäure. All die genannten Gruppen weisen eine Reaktivität mit Epoxidgruppen auf, wodurch das Poly(meth)acrylat vorteilhaft einer thermischen Vernetzung mit eingebrachten Epoxiden zugänglich wird. The glass transition temperature of the poly (meth) acrylates is preferably <0 ° C, more preferably between -20 and -50 ° C. The glass transition temperature of polymers or of polymer blocks in block copolymers is determined according to the invention by means of dynamic scanning calorimetry (DSC). For this purpose, approx. 5 mg of an untreated polymer sample are weighed into a small aluminum crucible (volume 25 ml) and closed with a perforated lid. A DSC 204 F1 from Netzsch is used for the measurement. It is carried out under nitrogen for the purpose of inerting. The sample is first cooled to -150 ° C, then heated to +150 ° C at a heating rate of 10 K / min and then cooled again to -150 ° C. The subsequent second heating curve is run again at 10 K / min and the change in heat capacity is recorded. Glass transitions are recognized as steps in the thermogram. The poly (meth) acrylate preferably contains at least one partially polymerized functional monomer, particularly preferably reactive with epoxy groups with the formation of a covalent bond. The proportionately polymerized functional monomer, particularly preferably reactive with epoxy groups with formation of a covalent bond, contains at least one functional group selected from the group consisting of carboxylic acid groups, sulfonic acid groups, phosphonic acid groups, hydroxyl groups, acid anhydride groups, epoxy groups and amino groups; in particular it contains at least one carboxylic acid group. The poly (meth) acrylate very preferably contains acrylic acid and / or methacrylic acid which has been partially polymerized into it. All of the groups mentioned have a reactivity with epoxy groups, as a result of which the poly (meth) acrylate is advantageously accessible to thermal crosslinking with introduced epoxides.
Das Poly(meth)acrylat lässt sich bevorzugt auf die folgende Monomerzusammensetzung zurückführen: a) mindestens ein Acrylsäureester und/oder Methacrylsäureester der folgenden Formel (1) The poly (meth) acrylate can preferably be attributed to the following monomer composition: a) at least one acrylic acid ester and / or methacrylic acid ester of the following formula (1)
CH2=C(RI)(COOR") (1 ), worin R' = H oder CH3 und R" ein Alkylrest mit 4 bis 18 C-Atomen ist; b) mindestens ein olefinisch ungesättigtes Monomer mit mindestens einer funktionellenCH 2 = C (R I ) (COOR ") (1), in which R '= H or CH 3 and R" is an alkyl radical having 4 to 18 carbon atoms; b) at least one olefinically unsaturated monomer with at least one functional
Gruppe ausgewählt aus der Gruppe bestehend aus Carbonsäuregruppen, Sulfonsäuregruppen, Phosphonsäuregruppen, Hydroxygruppen,Group selected from the group consisting of carboxylic acid groups, sulfonic acid groups, phosphonic acid groups, hydroxyl groups,
Säureanhydridgruppen, Epoxidgruppen und Aminogruppen; c) optional weitere Acrylsäureester und/oder Methacrylsäureester und/oder olefinisch ungesättigte Monomere, die mit der Komponente (a) copolymerisierbar sind. Acid anhydride groups, epoxy groups and amino groups; c) optionally further acrylic acid esters and / or methacrylic acid esters and / or olefinically unsaturated monomers which are copolymerizable with component (a).
Es ist besonders vorteilhaft, die Monomere der Komponente a) mit einem Anteil von 45 bis 99 Gew.-%, die Monomere der Komponente b) mit einem Anteil von 1 bis 15 Gew.-% und die Monomere der Komponente c) mit einem Anteil von 0 bis 40 Gew.-% zu wählen, wobei die Angaben auf die Monomermischung für das Basispolymer ohne Zusätze eventueller Additive wie Harze etc. bezogen sind. It is particularly advantageous to use the monomers of component a) in a proportion of 45 to 99% by weight, the monomers of component b) in a proportion of 1 to 15% by weight and the monomers of component c) in a proportion from 0 to 40% by weight to be selected, the information being based on the monomer mixture for the base polymer without the addition of any additives such as resins, etc.
Besonders bevorzugt lässt sich das Poly(meth)acrylat auf die folgende Monomerzusammensetzung zurückgeführt werden: The poly (meth) acrylate can particularly preferably be attributed to the following monomer composition:
65 bis 99 Gew.-% 2-Ethylhexylacrylat und/oder n-Butylacrylat, 65 to 99% by weight of 2-ethylhexyl acrylate and / or n-butyl acrylate,
0 bis 30 Gew.-% Methylacrylat, 1 bis 15 Gew.-% Acrylsäure. 0 to 30% by weight methyl acrylate, 1 to 15% by weight acrylic acid.
Die Herstellung des Poly(meth)acrylats oder der Poly(meth)acrylate erfolgt bevorzugt durch konventionelle radikalische Polymerisationen oder kontrollierte radikalische Polymerisationen. Die Poly(meth)acrylate können durch Copolymerisation der Monomere unter Verwendung üblicher Polymerisationsinitiatoren sowie gegebenenfalls von Reglern hergestellt werden, wobei bei den üblichen Temperaturen in Substanz, in Emulsion, zum Beispiel in Wasser oder flüssigen Kohlenwasserstoffen, oder in Lösung polymerisiert wird. The poly (meth) acrylate or the poly (meth) acrylates are preferably prepared by conventional free-radical polymerizations or controlled free-radical polymerizations. The poly (meth) acrylates can be prepared by copolymerizing the monomers using customary polymerization initiators and, if appropriate, regulators, polymerizing at the customary temperatures in bulk, in emulsion, for example in water or liquid hydrocarbons, or in solution.
Bevorzugt werden die Poly(meth)acrylate durch Copolymerisation der Monomere in Lösungsmitteln, besonders bevorzugt in Lösungsmitteln mit einem Siedebereich von 50 bis 150 °C, insbesondere von 60 bis 120 °C, unter Verwendung von 0,01 bis 5 Gew.-%, insbesondere von 0,1 bis 2 Gew.-%, jeweils bezogen auf das Gesamtgewicht der Monomeren, an Polymerisationsinitiatoren hergestellt. The poly (meth) acrylates are preferred by copolymerizing the monomers in solvents, particularly preferably in solvents with a boiling range from 50 to 150 ° C., in particular from 60 to 120 ° C., using 0.01 to 5% by weight, in particular from 0.1 to 2% by weight, based in each case on the total weight of the monomers, of polymerization initiators.
Prinzipiell eignen sich alle üblichen Initiatoren. Beispiele für Radikalquellen sind Peroxide, Hydroperoxide und Azoverbindungen, zum Beispiel Dibenzoylperoxid, Cumolhydroperoxid, Cyclohexanonperoxid, Di-t-butylperoxid, Cyclohexylsulfonylacetylperoxid,In principle, all customary initiators are suitable. Examples of radical sources are peroxides, hydroperoxides and azo compounds, for example dibenzoyl peroxide, cumene hydroperoxide, cyclohexanone peroxide, di-t-butyl peroxide, cyclohexylsulfonylacetyl peroxide,
Diisopropylpercarbonat, t-Butylperoktoat und Benzpinacol. Bevorzugte radikalische Initiatoren sind 2,2'-Azobis(2-methylbutyronitril) (Vazo® 67™ der Firma DuPont) oder 2,2’-Azobis(2- methylpropionitril) (2,2’-Azobisisobutyronitril; AIBN; Vazo® 64™ der Firma DuPont). Diisopropyl percarbonate, t-butyl peroctoate, and benzpinacol. Preferred free-radical initiators are 2,2'-azobis (2-methylbutyronitrile) (Vazo® 67 ™ from DuPont) or 2,2'-azobis (2-methylpropionitrile) (2,2'-azobisisobutyronitrile; AIBN; Vazo® 64 ™ from DuPont).
Bevorzugte Lösungsmittel für die Herstellung der Poly(meth)acrylate sind Alkohole wie Methanol, Ethanol, n- und iso-Propanol, n- und iso-Butanol, insbesondere Isopropanol und/oder Isobutanol; Kohlenwasserstoffe wie Toluol und insbesondere Benzine eines Siedebereichs von 60 bis 120 °C; Ketone, insbesondere Aceton, Methylethylketon, Methylisobutylketon; Ester wie Essigsäureethylester sowie Gemische der vorstehend genannten Lösungsmittel. Besonders bevorzugte Lösungsmittel sind Gemische, die Isopropanol in Mengen von 2 bis 15 Gew.-%, insbesondere von 3 bis 10 Gew.-%, jeweils bezogen auf das eingesetzte Lösungsmittelgemisch, enthalten. Preferred solvents for the preparation of the poly (meth) acrylates are alcohols such as methanol, ethanol, n- and iso-propanol, n- and iso-butanol, in particular isopropanol and / or isobutanol; Hydrocarbons such as toluene and, in particular, gasolines with a boiling range from 60 to 120 ° C .; Ketones, especially acetone, methyl ethyl ketone, methyl isobutyl ketone; Esters such as ethyl acetate and mixtures of the abovementioned solvents. Particularly preferred solvents are mixtures which contain isopropanol in amounts of from 2 to 15% by weight, in particular from 3 to 10% by weight, based in each case on the solvent mixture used.
Bevorzugt erfolgt nach der Herstellung (Polymerisation) der Poly(meth)acrylate eine Aufkonzentration, und die weitere Verarbeitung der Poly(meth)acrylate erfolgt im Wesentlichen lösemittelfrei. Die Aufkonzentration des Polymerisats kann in Abwesenheit von Vernetzer- und Beschleunigersubstanzen geschehen. Es ist aber auch möglich, eine dieser Verbindungsklassen dem Polymerisat bereits vor der Aufkonzentration zuzusetzen, so dass die Aufkonzentration dann in Gegenwart dieser Substanz(en) erfolgt. Preferably, after the production (polymerization) of the poly (meth) acrylates, there is a concentration, and the further processing of the poly (meth) acrylates is essentially solvent-free. The polymer can be concentrated in the absence of crosslinking and accelerating substances. However, it is also possible to add one of these classes of compound to the polymer even before the concentration, so that the concentration then takes place in the presence of this substance (s).
Die Polymerisate können nach dem Aufkonzentrationsschritt in einen Compounder überführt werden. Gegebenenfalls können die Aufkonzentration und die Compoundierung auch im selben Reaktor stattfinden. Die weitere Verarbeitung nach der Aufkonzentration (Compoundierung) findet bevorzugt in einem oder mehreren Extrudern statt. Die Masse wird dabei aus der Schmelze auf ein ggf. temporäres Trägermaterial aufgebracht und mittels Kalanderwalzen zu einer Schicht ausgeformt. After the concentration step, the polymers can be transferred to a compounder. If necessary, the concentration and the compounding can also take place in the same reactor. Further processing after the concentration (Compounding) takes place preferably in one or more extruders. The mass is applied from the melt to an optionally temporary carrier material and formed into a layer by means of calender rollers.
Die gewichtsmittleren Molekulargewichte Mwder Poly(meth)acrylate liegen bevorzugt in einem Bereich von 20.000 bis 2.000.000 g/mol; sehr bevorzugt in einem Bereich von 100.000 bis 1.500.000 g/mol, äußerst bevorzugt in einem Bereich von 150.000 bis 1.000.000 g/mol. Dazu kann es vorteilhaft sein, die Polymerisation in Gegenwart geeigneter Polymerisationsregler wie Thiole, Halogenverbindungen und/oder Alkohole durchzuführen, um das gewünschte mittlere Molekulargewicht einzustellen. The weight-average molecular weights M w of the poly (meth) acrylates are preferably in a range from 20,000 to 2,000,000 g / mol; very preferably in a range from 100,000 to 1,500,000 g / mol, extremely preferably in a range from 150,000 to 1,000,000 g / mol. For this purpose it can be advantageous to carry out the polymerization in the presence of suitable polymerization regulators such as thiols, halogen compounds and / or alcohols in order to set the desired average molecular weight.
Die Angaben der zahlenmittleren Molmasse Mn und der gewichtsmittleren Molmasse Mw in dieser Schrift beziehen sich auf die an sich bekannte Bestimmung per Gelpermeationschromatographie (GPC). Die Bestimmung erfolgt an 100 mI klarfiltrierter Probe (Probenkonzentration 4 g/l). Als Eluent wird Tetrahydrofuran mit 0,1 Vol.-% Trifluoressigsäure eingesetzt. Die Messung erfolgt bei 25 °C. The details of the number-average molar mass M n and the weight-average molar mass M w in this document relate to the known determination by gel permeation chromatography (GPC). The determination is carried out on 100 ml clear-filtered sample (sample concentration 4 g / l). Tetrahydrofuran with 0.1% by volume of trifluoroacetic acid is used as the eluent. The measurement takes place at 25 ° C.
Als Vorsäule wird eine Säule Typ PSS-SDV, 5 pm, 103 Ä, 8,0 mm * 50 mm (Angaben hier und im Folgenden in der Reihenfolge: Typ, Partikelgrösse, Porosität, Innendurchmesser * Länge; 1 Ä = 10 1° m) verwendet. Zur Auftrennung wird eine Kombination der Säulen des Typs PSS- SDV, 5 pm, 103 Ä sowie 105 Ä und 106 Ä mit jeweils 8,0 mm * 300 mm eingesetzt (Säulen der Firma Polymer Standards Service; Detektion mittels Differentialrefraktometer Shodex RI71). Die Durchflussmenge beträgt 1 ,0 ml pro Minute. Die Kalibrierung erfolgt bei Poly(meth)acrylaten gegen PMMA-Standards (Polymethylmethacrylat-Kalibrierung) und sonst (Harze, Elastomere) gegen PS-Standards (Polystyrol-Kalibrierung). A column type PSS-SDV, 5 μm, 10 3 Å, 8.0 mm * 50 mm (details here and below in the order: type, particle size, porosity, inner diameter * length; 1 Å = 10 1 ° m) used. A combination of columns of the PSS-SDV, 5 pm, 10 3 Å, as well as 10 5 Å and 10 6 Å, each 8.0 mm * 300 mm, is used for separation (columns from Polymer Standards Service; detection using a Shodex RI71 differential refractometer ). The flow rate is 1.0 ml per minute. In the case of poly (meth) acrylates, calibration is carried out against PMMA standards (polymethyl methacrylate calibration) and otherwise (resins, elastomers) against PS standards (polystyrene calibration).
Bevorzugt weist das Poly(meth)acrylat eine Polydispersität PD < 4 und somit eine relativ enge Molekulargewichtsverteilung auf. Darauf basierende Massen haben trotz eines relativ niedrigen Molekulargewichts nach dem Vernetzen eine besonders gute Scherfestigkeit. Zudem ermöglicht die niedrigere Polydispersität eine leichtere Verarbeitung aus der Schmelze, da die Fließviskosität gegenüber einem breiter verteilten Poly(meth)acrylat bei weitgehend gleichen Anwendungseigenschaften geringer ist. Eng verteilte Poly(meth)acrylate können vorteilhaft durch anionische Polymerisation oder durch kontrollierte radikalische Polymerisationsmethoden hergestellt werden, wobei letztere besonders gut geeignet sind. Auch über N-Oxyle lassen sich entsprechende Poly(meth)acrylate hersteilen. Ferner lässt sich in vorteilhafter Weise die Atom Transfer Radical Polymerization (ATRP) zur Synthese eng verteilter Poly(meth)acrylate einsetzen, wobei als Initiator bevorzugt monofunktionelle oder difunktionelle sekundäre oder tertiäre Halogenide und zur Abstraktion der Halogenide Cu-, Ni- , Fe-, Pd-, Pt-, Ru-, Os-, Rh-, Co-, Ir-, Ag- oder Au-Komplexe eingesetzt werden. Auch RAFT- Polymerisation ist geeignet. Die Poly(meth)acrylate sind bevorzugt durch Verknüpfungsreaktionen - insbesondere im Sinne von Additions- oder Substitutionsreaktionen - von in ihnen enthaltenen funktionellen Gruppen mit thermischen Vernetzern vernetzt. Es können alle thermischen Vernetzer verwendet werden, die The poly (meth) acrylate preferably has a polydispersity PD <4 and thus a relatively narrow molecular weight distribution. In spite of a relatively low molecular weight, compositions based thereon have a particularly good shear strength after crosslinking. In addition, the lower polydispersity enables easier processing from the melt, since the flow viscosity is lower than that of a more widely distributed poly (meth) acrylate with largely the same application properties. Narrowly distributed poly (meth) acrylates can advantageously be prepared by anionic polymerization or by controlled radical polymerization methods, the latter being particularly suitable. Corresponding poly (meth) acrylates can also be produced via N-oxyls. Furthermore, atom transfer radical polymerization (ATRP) can advantageously be used for the synthesis of narrowly distributed poly (meth) acrylates, the initiator preferably being monofunctional or difunctional secondary or tertiary halides and, for the abstraction of the halides, Cu, Ni, Fe, Pd, Pt, Ru, Os-, Rh-, Co-, Ir-, Ag- or Au complexes can be used. RAFT polymerization is also suitable. The poly (meth) acrylates are preferably crosslinked by linking reactions - in particular in the sense of addition or substitution reactions - of functional groups contained in them with thermal crosslinkers. All thermal crosslinkers can be used that
- sowohl eine ausreichend lange Verarbeitungszeit gewährleisten, sodass es nicht zu einer Vergelung während des Verarbeitungsprozesses, insbesondere des Extrusionsprozesses, kommt, - ensure a sufficiently long processing time so that gelation does not occur during the processing process, in particular the extrusion process,
- als auch zu einer schnellen Nachvernetzung des Polymers auf den gewünschten Vernetzungsgrad bei niedrigeren Temperaturen als der Verarbeitungstemperatur, insbesondere bei Raumtemperatur, führen. - As well as lead to rapid post-crosslinking of the polymer to the desired degree of crosslinking at temperatures lower than the processing temperature, in particular at room temperature.
Bevorzugt werden thermische Vernetzer zu 0,1 bis 5 Gew.-%, insbesondere zu 0,2 bis 1 Gew.- %, bezogen auf die Gesamtmenge des zu vernetzenden Polymers, eingesetzt. Thermal crosslinkers are preferably used in an amount of from 0.1 to 5% by weight, in particular from 0.2 to 1% by weight, based on the total amount of the polymer to be crosslinked.
Auch eine Vernetzung über Komplexbildner, auch als Chelate bezeichnet, ist möglich. Ein bevorzugter Komplexbildner ist beispielsweise Aluminiumacetylacetonat. Crosslinking via complexing agents, also known as chelates, is also possible. A preferred complexing agent is, for example, aluminum acetylacetonate.
Bevorzugt sind die Poly(meth)acrylate mittels Epoxid(en) bzw. mittels einer oder mehrerer epoxidgruppenhaltigen Substanz(en) vernetzt. Bei den epoxidgruppenhaltigen Substanzen handelt es sich insbesondere um multifunktionelle Epoxide, also solche mit zumindest zwei Epoxidgruppen; entsprechend kommt es insgesamt zu einer mittelbaren Verknüpfung der die funktionellen Gruppen tragenden Bausteine der Poly(meth)acrylate. Die epoxidgruppenhaltigen Substanzen können sowohl aromatische als auch aliphatische Verbindungen sein. The poly (meth) acrylates are preferably crosslinked by means of epoxide (s) or by means of one or more substance (s) containing epoxide groups. The substances containing epoxy groups are in particular multifunctional epoxides, that is to say those with at least two epoxy groups; accordingly, overall there is an indirect linkage of the building blocks of the poly (meth) acrylates which carry the functional groups. The substances containing epoxy groups can be both aromatic and aliphatic compounds.
Bevorzugte Epoxid-Vernetzer sind z.B. cycloaliphatische Epoxide wie 3,4- Epoxycyclohexylmethyl-3,4-epoxycyclohexancarboxylat (UVACure1500). Preferred epoxy crosslinkers are, for example, cycloaliphatic epoxides such as 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (UVACure1500).
Besonders bevorzugt sind die Poly(meth)acrylate mittels eines Vernetzer-Beschleuniger- Systems („Vernetzungssystem“) vernetzt, um eine bessere Kontrolle sowohl über die Verarbeitungszeit, die Vernetzungskinetik sowie den Vernetzungsgrad zu erhalten. Das Vernetzer-Beschleuniger-System umfasst bevorzugt zumindest eine epoxidgruppenhaltige Substanz als Vernetzer und zumindest eine bei einer Temperatur unterhalb der Schmelztemperatur des zu vernetzenden Polymers für Vernetzungsreaktionen mittels epoxidgruppenhaltiger Verbindungen beschleunigend wirkende Substanz als Beschleuniger.The poly (meth) acrylates are particularly preferably crosslinked by means of a crosslinker-accelerator system (“crosslinking system”) in order to obtain better control over the processing time, the crosslinking kinetics and the degree of crosslinking. The crosslinker-accelerator system preferably comprises at least one substance containing epoxy groups as crosslinker and at least one substance that accelerates crosslinking reactions by means of compounds containing epoxy groups at a temperature below the melting temperature of the polymer to be crosslinked.
Als Beschleuniger werden besonders bevorzugt Amine eingesetzt. In einer weiteren Ausführungsform III der Polymerschaumschicht enthält die Polymerschaumschicht, insbesondere das Matrixmaterial der Polymerschaumschicht, mindestens ein Vinylaromatenblockcopolymer. Bevorzugt enthält die Polymerschaumschicht, insbesondere das Matrixmaterial der Polymerschaumschicht, mindestens ein Vinylaromatenblockcopolymer, das mindestens einen Polymerblock A enthält, der überwiegend durch Polymerisation von Vinylaromaten gebildet ist, und mindestens einen Polymerblock B enthält, der überwiegend durch Polymerisation von konjugierten Dienen gebildet ist, wobei der Anteil an 1 ,2-verknüpftem konjugiertem Dien im B- Block weniger als 30 Gew.-% beträgt, vorzugsweise weniger als 20 Gew.-% (bestimmbar mittels 1H-NMR). Amines are particularly preferably used as accelerators. In a further embodiment III of the polymer foam layer, the polymer foam layer, in particular the matrix material of the polymer foam layer, contains at least one vinyl aromatic block copolymer. The polymer foam layer, in particular the matrix material of the polymer foam layer, preferably contains at least one vinyl aromatic block copolymer which contains at least one polymer block A which is predominantly formed by the polymerization of vinyl aromatic compounds and at least one polymer block B which is predominantly formed by the polymerization of conjugated dienes, the The proportion of 1,2-linked conjugated diene in the B block is less than 30% by weight, preferably less than 20% by weight (can be determined by means of 1 H-NMR).
Das vorstehend beschriebene Vinylaromatenblockcopolymer ist in der hier betrachteten Ausführungsform III im Polymerschaum bevorzugt als Elastomerkomponente enthalten. Sofern der Polymerschaum mehrere Elastomerkomponenten enthält, ist es im Polymerschaum bevorzugt zu mindestens 50 Gew.-%, bezogen auf das Gesamtgewicht aller Elastomerkomponenten, enthalten. The vinyl aromatic block copolymer described above is preferably contained in the polymer foam as an elastomer component in embodiment III considered here. If the polymer foam contains several elastomer components, it is preferably contained in the polymer foam to an extent of at least 50% by weight, based on the total weight of all elastomer components.
Der Polymerblock A des bevorzugten Vinylaromatenblockcopolymers ist überwiegend durch Polymerisation von Vinylaromaten gebildet. Das bedeutet, dass der Block A typischerweise aus einer Polymerisation hervorgegangen ist, bei der mehr als 50 Gew.-% der eingesetzten Monomere Vinylaromaten sind. Stärker bevorzugt ist der Polymerblock A aus einer Polymerisation hervorgegangen, bei der als Monomere ausschließlich Vinylaromaten eingesetzt worden sind. The polymer block A of the preferred vinyl aromatic block copolymer is formed predominantly by the polymerization of vinyl aromatic compounds. This means that the block A typically emerged from a polymerization in which more than 50% by weight of the monomers used are vinyl aromatics. More preferably, the polymer block A emerged from a polymerization in which exclusively vinyl aromatics were used as monomers.
Der Polymerblock B des bevorzugten Vinylaromatenblockcopolymers ist überwiegend durch Polymerisation von konjugierten Dienen gebildet. Das bedeutet, dass der Block B aus einer Polymerisation hervorgegangen ist, bei der mehr als 50 Gew.-% der eingesetzten Monomere konjugierte Diene sind. Stärker bevorzugt ist der Polymerblock B aus einer Polymerisation hervorgegangen, bei der als Monomere ausschließlich konjugierte Diene eingesetzt worden sind. The polymer block B of the preferred vinyl aromatic block copolymer is formed predominantly by the polymerization of conjugated dienes. This means that block B emerged from a polymerization in which more than 50% by weight of the monomers used are conjugated dienes. More preferably, the polymer block B emerged from a polymerization in which exclusively conjugated dienes were used as monomers.
Der Anteil an 1 ,2-verknüpftem konjugiertem Dien im B-Block des bevorzugten Vinylaromatenblockcopolymers beträgt weniger als 30 Gew.-%, vorzugsweise weniger als 20 Gew.-%. Stärker bevorzugt beträgt dieser Anteil weniger als 15 Gew.-%, insbesondere 8 bis 12 Gew.-%. Mit dem Anteil an 1 ,2-verknüpftem konjugiertem Dien im B-Block ist der Gewichtsanteil an konjugiertem Dien, das durch 1 ,2-Addition (im Gegensatz zur 1 ,4-Addition) einpolymerisiert worden ist, gemeint, bezogen auf die bei der Herstellung des Polymerblocks B eingesetzte gesamte Monomermasse. Die 1 ,2-Addition von konjugiertem Dien führt zu einer vinylischen Seitengruppe im Polymerblock B, während die 1 ,4-Addition von konjugiertem Dien zu einer vinylischen Funktionalität in der Hauptkette des Polymerblocks B führt. Mit der 1 ,2- Addition eines konjugierten Diens ist somit gemeint, dass der Einbau des Monomers in die Polymerkette entweder über die Positionen C1 und C2 oder über die Positionen C3 und C4 (zum Beispiel im Fall von Isopren als konjugiertem Dien) verläuft. Bei der 1 ,4-Addition eines konjugierten Diens dagegen verläuft er über die Positionen C1 und C4. The proportion of 1,2-linked conjugated diene in the B block of the preferred vinyl aromatic block copolymer is less than 30% by weight, preferably less than 20% by weight. This proportion is more preferably less than 15% by weight, in particular 8 to 12% by weight. The proportion of 1,2-linked conjugated diene in the B block is the proportion by weight of conjugated diene which has been polymerized by 1,2 addition (as opposed to 1,4 addition), based on the Production of the polymer block B total monomer mass used. The 1,2 addition of conjugated diene results in a vinylic side group in the polymer block B, while the 1,4-addition of conjugated diene leads to a vinylic functionality in the main chain of the polymer block B. The 1,2 addition of a conjugated diene thus means that the incorporation of the monomer into the polymer chain takes place either via positions C1 and C2 or via positions C3 and C4 (for example in the case of isoprene as conjugated diene). In the 1,4-addition of a conjugated diene, on the other hand, it runs through positions C1 and C4.
Das Vinylaromatenblockcopolymer weist bevorzugt einen Aufbau A-B, A-B-A, (A-B)n, (A-B)nX oder (A-B-A)nX auf, worin die Blöcke A unabhängig voneinander für ein Polymer, gebildet durch Polymerisation mindestens eines Vinylaromaten, die Blöcke B unabhängig voneinander für ein Polymer, gebildet durch Polymerisation von konjugierten Dienen mit 4 bis 18 C-Atomen, The vinyl aromatic block copolymer preferably has a structure AB, ABA, (AB) n , (AB) n X or (ABA) nX, in which the blocks A independently of one another for a polymer formed by polymerization of at least one vinyl aromatic, the blocks B independently of one another for a polymer formed by the polymerization of conjugated dienes with 4 to 18 carbon atoms,
X für den Rest eines Kopplungsreagenzes oder Initiators und n für eine ganze Zahl > 2 stehen. X stands for the remainder of a coupling reagent or initiator and n stands for an integer> 2.
Besonders bevorzugt sind in der Ausführungsform III alle Vinylaromatenblockcopolymere der erfindungsgemäßen Polymerschaumschicht Blockcopolymere mit einem Aufbau A-B, A-B-A, (A-B)n, (A-B)nX oder (A-B-A)nX wie vorstehend dargelegt. Die Polymerschaumschicht kann somit auch Gemische verschiedener Vinylaromatenblockcopolymere mit einem Aufbau wie vorstehend beschrieben enthalten. Particularly preferred in embodiment III are all vinyl aromatic block copolymers of the polymer foam layer according to the invention block copolymers with a structure AB, ABA, (AB) n, (AB) nX or (ABA) n X as set out above. The polymer foam layer can thus also contain mixtures of different vinyl aromatic block copolymers with a structure as described above.
Die Blöcke B werden auch als gummiartige Blöcke oder Weichblöcke bezeichnet und die Blöcke A als glasartige Blöcke oder Hartblöcke. Besonders bevorzugt weist mindestens ein Vinylaromatenblockcopolymer der Polymerschaumschicht einen Aufbau A-B, A-B-A, (A-B)2X, (A-B)3X oder (A-B)4X auf, wobei für A, B und X die vorstehenden Bedeutungen gelten. Ganz besonders bevorzugt weisen alle Vinylaromatenblockcopolymere einen Aufbau A-B, A-B-A, (A-B)2X, (A-B)3X oder (A-B)4X auf, wobei für A, B und X die vorstehenden Bedeutungen gelten. Insbesondere enthält in der Ausführungsform III die Polymerschaumschicht ein Gemisch aus Blockcopolymeren mit einem Aufbau A-B, A-B-A, (A-B)2X, (A-B)sX oder (A-B)4X, das stärker bevorzugt mindestens Diblockcopolymere A-B und/oder Triblockcopolymere A-B-A und/oder (A-B)2X enthält, insbesondere ein Gemisch aus Diblockcopolymeren (A-B) und Triblockcopolymeren (A-B-A), beispielsweise aus zwei Sorten Vinylaromatenblockcopolymer mit einem unterschiedlichen Gewichtsverhältnis an Diblockcopolymeren (A-B) und Triblockcopolymeren (A-B-A). Die Vinylaromatenblockcopolymere weisen bevorzugt einen Diblockcopolymeranteil von 0 Gew.-% bis 70 Gew.-%, stärker bevorzugt von 15 Gew.-% bis 65 Gew.-%, insbesondere von 30 bis 60 Gew.-%, ganz besonders bevorzugt von 40 bis 60 Gew.-%, beispielsweise von 51 ,5 Gew.-% bis 55 Gew.-% auf. The blocks B are also referred to as rubber-like blocks or soft blocks and the blocks A as glass-like blocks or hard blocks. Particularly preferably, at least one vinyl aromatic block copolymer of the polymer foam layer has a structure AB, ABA, (AB) 2X, (AB) 3X or (AB) 4 X, where A, B and X are as defined above. All vinylaromatic block copolymers very particularly preferably have a structure AB, ABA, (AB) 2X, (AB) 3X or (AB) 4 X, where A, B and X are as defined above. In particular, in embodiment III, the polymer foam layer contains a mixture of block copolymers with a structure AB, ABA, (AB) 2X, (AB) sX or (AB) 4 X, which is more preferably at least diblock copolymers AB and / or triblock copolymers ABA and / or ( AB) 2X contains, in particular, a mixture of diblock copolymers (AB) and triblock copolymers (ABA), for example of two types of vinyl aromatic block copolymers with a different weight ratio of diblock copolymers (AB) and triblock copolymers (ABA). The vinyl aromatic block copolymers preferably have a diblock copolymer content of 0% by weight to 70% by weight, more preferably from 15% by weight to 65% by weight, in particular from 30 to 60% by weight, very particularly preferably from 40 to 60% by weight, for example from 51.5% by weight to 55% by weight.
Die aus den A- und B-Blöcken resultierenden Blockcopolymere können gleiche oder unterschiedliche B-Blöcke enthalten. The block copolymers resulting from the A and B blocks can contain the same or different B blocks.
In bevorzugten Vinylaromatenblockcopolymeren, insbesondere in bevorzugten Styrolblockcopolymeren, beträgt der Anteil an Polyvinylaromaten, insbesondere an Polystyrol, bevorzugt mindestens 12 Gew.-%, stärker bevorzugt mindestens 18 Gew.-%, besonders bevorzugt mindestens 25 Gew.-% und ebenso bevorzugt höchstens 45 Gew.-% und stärker bevorzugt höchstens 35 Gew. -%. In preferred vinyl aromatic block copolymers, in particular in preferred styrene block copolymers, the proportion of polyvinyl aromatics, in particular of polystyrene, is preferably at least 12% by weight, more preferably at least 18% by weight, particularly preferably at least 25% by weight and also preferably at most 45% by weight % and more preferably at most 35% by weight.
Anstelle der bevorzugten Polystyrolblöcke können als Vinylaromaten auch Polymerblöcke auf Basis anderer aromatenhaltiger Homo- und Copolymere mit Glasübergangstemperaturen von größer 75 °C genutzt werden. Bevorzugt sind Homo- und/oder Copolymerblöcke auf Basis von C8- bis C12-Aromaten wie zum Beispiel a-Methylstyrol. Es können gleiche oder unterschiedliche A-Blöcke enthalten sein. Instead of the preferred polystyrene blocks, polymer blocks based on other aromatic-containing homopolymers and copolymers with glass transition temperatures of greater than 75 ° C. can also be used as vinyl aromatics. Preference is given to homo- and / or copolymer blocks based on C8 to C12 aromatics, such as, for example, α-methylstyrene. It can contain the same or different A-blocks.
Vorzugsweise ist der Polymerblock A überwiegend durch Polymerisation von Styrol und/oder a-Methylstyrol gebildet. Der Block A kann somit als Homo- oder Copolymer vorliegen. Besonders bevorzugt ist der Block A ein Polystyrol. Ganz besonders bevorzugt weisen die Vinylaromatenblockcopolymere Polystyrolendblöcke auf. The polymer block A is preferably formed predominantly by the polymerization of styrene and / or α-methylstyrene. The block A can thus be present as a homo- or copolymer. Block A is particularly preferably a polystyrene. The vinyl aromatic block copolymers very particularly preferably have polystyrene end blocks.
Der Polymerblock B ist vorzugsweise überwiegend durch Polymerisation von konjugierten Dienen ausgewählt aus der Gruppe bestehend aus Butadien, Isopren, Ethylbutadien, Phenylbutadien, Pentadien, Hexadien, Ethylhexadien, Dimethylbutadien, a-Farnesen und ß- Farnesen sowie beliebigen Mischungen dieser Monomere gebildet; er kann ebenso wie der Block A als Homopolymer oder als Copolymer vorliegen. Besonders bevorzugt ist der Block B überwiegend durch Polymerisation von Butadien und/oder Isopren gebildet. Ganz besonders bevorzugt ist der Block B ein Polybutadien; dieses weist im Vergleich zu Polyisopren ein noch besseres Alterungsverhalten auf. The polymer block B is preferably formed predominantly by polymerization of conjugated dienes selected from the group consisting of butadiene, isoprene, ethylbutadiene, phenylbutadiene, pentadiene, hexadiene, ethylhexadiene, dimethylbutadiene, α-farneses and β-farneses and any mixtures of these monomers; like block A, it can be present as a homopolymer or as a copolymer. Block B is particularly preferably formed predominantly by polymerizing butadiene and / or isoprene. Block B is very particularly preferably a polybutadiene; this shows an even better aging behavior compared to polyisoprene.
A-Blöcke werden im Zusammenhang dieser Erfindung auch als „Hartblöcke“ bezeichnet. B- Blöcke werden entsprechend auch „Weichblöcke“ oder „Elastomerblöcke“ genannt. Dies spiegelt die Auswahl der Blöcke entsprechend ihrer Glasübergangstemperaturen wieder, die für die A-Blöcke bevorzugt mindestens 25 °C, insbesondere mindestens 50 °C beträgt und für B-Blöcke bevorzugt höchstens 25 °C, besonders bevorzugt höchstens -25 °C, und insbesondere höchstens -50 °C beträgt. A blocks are also referred to as “hard blocks” in the context of this invention. B blocks are also called “soft blocks” or “elastomer blocks”. This reflects the selection of the blocks according to their glass transition temperatures, which for the A blocks is preferably at least 25 ° C., in particular at least 50 ° C., and for B blocks is preferably at most 25 ° C, particularly preferably at most -25 ° C, and in particular at most -50 ° C.
In der Ausführungsform III beträgt der Anteil der Gesamtheit der Vinylaromatenblockcopolymere, insbesondere der Styrolblockcopolymere, an der Polymerschaumschicht bevorzugt mindestens 35 Gew.-%, bezogen auf das Gesamtgewicht der Polymerschaumschicht. Ein solcher Anteil verbessert vorteilhaft die Kohäsion der Polymerschaumschicht. In embodiment III, the proportion of all the vinyl aromatic block copolymers, in particular the styrene block copolymers, in the polymer foam layer is preferably at least 35% by weight, based on the total weight of the polymer foam layer. Such a proportion advantageously improves the cohesion of the polymer foam layer.
Der maximale Anteil der Gesamtheit der Vinylaromatenblockcopolymere, insbesondere der Styrolblockcopolymere, an der Polymerschaumschicht beträgt bevorzugt maximal 75 Gew.-%, insbesondere maximal 65 Gew.-%, ganz besonders bevorzugt maximal 55 Gew.-%. The maximum proportion of all of the vinyl aromatic block copolymers, in particular the styrene block copolymers, in the polymer foam layer is preferably a maximum of 75% by weight, in particular a maximum of 65% by weight, very particularly preferably a maximum of 55% by weight.
Der Polymerschaum der Ausführungsform III enthält bevorzugt mindestens ein Klebharz. Grundsätzlich können ein oder mehrere Klebharze enthalten sein. Damit werden dem Schaum vorteilhaft haftklebrige Eigenschaften verliehen. The polymer foam of embodiment III preferably contains at least one adhesive resin. In principle, one or more tackifier resins can be included. In this way, the foam is advantageously given pressure-sensitive adhesive properties.
Unter einem „Klebharz“ wird entsprechend dem allgemeinem Fachmannverständnis ein niedermolekulares, Oligomeres oder polymeres Harz verstanden, das die Adhäsion (den Tack, die Eigenklebrigkeit) der Haftklebemasse im Vergleich zu der kein Klebharz enthaltenden, ansonsten aber identischen Haftklebemasse erhöht. According to the general understanding of the art, an “adhesive resin” is understood to mean a low molecular weight, oligomeric or polymeric resin which increases the adhesion (the tack, the inherent tack) of the PSA in comparison to the PSA which does not contain adhesive resin but is otherwise identical.
Das Klebharz weist bevorzugt einen DACP (diacetone alcohol cloud point) von > 0 °C, stärker bevorzugt von > 10 °C, insbesondere von > 30 °C, und eine Erweichungstemperatur (Ring & Ball) von > 70 °C, vorzugsweise von > 100 °C auf. The adhesive resin preferably has a DACP (diacetone alcohol cloud point) of> 0 ° C, more preferably> 10 ° C, in particular> 30 ° C, and a softening temperature (ring & ball) of> 70 ° C, preferably> 100 ° C.
Besonders bevorzugt weist das jeweilige Klebharz einen DACP-Wert von maximal 45 °C, sofern keine Isoprenblöcke in der Elastomerphase vorliegen, oder von maximal 60 °C, sofern Isoprenblöcke in der Elastomerphase vorliegen, auf. Die Erweichungstemperatur des jeweiligen Klebharzes beträgt besonders bevorzugt maximal 150 °C. The respective adhesive resin particularly preferably has a DACP value of a maximum of 45 ° C. if there are no isoprene blocks in the elastomer phase, or of a maximum of 60 ° C. if there are isoprene blocks in the elastomer phase. The softening temperature of the respective adhesive resin is particularly preferably a maximum of 150.degree.
Bevorzugt ist das Klebharz ein Kohlenwasserstoffharz; insbesondere ist es ausgewählt aus der Gruppe bestehend aus hydrierten und nicht hydrierten Polymerisaten des Dicyclopentadiens, nicht hydrierten, partiell, selektiv oder vollständig hydrierten Kohlenwasserstoffharzen auf Basis von C5-, C5/C9- oder C9-Monomerströmen und Polyterpenharzen auf Basis von a-Pinen und/oder ß-Pinen und/oder d-Limonen. Diese Klebharze können sowohl allein als auch im Gemisch eingesetzt werden. Es können grundsätzlich sowohl bei Raumtemperatur feste als auch flüssige Harze zum Einsatz kommen. Klebharze, hydriert oder nicht hydriert, die auch Sauerstoff enthalten, können optional bis zu einem maximalen Anteil von 25 Gew.-%, bezogen auf die Gesamtmasse der im Polymerschaum enthaltenen Klebharze, im Polymerschaum der Ausführungsform III enthalten sein, so zum Beispiel Kolophonium- und/oder Kolophoniumesterharze und/oder Terpenphenolharze. Preferably the adhesive resin is a hydrocarbon resin; In particular, it is selected from the group consisting of hydrogenated and non-hydrogenated polymers of dicyclopentadiene, non-hydrogenated, partially, selectively or fully hydrogenated hydrocarbon resins based on C5, C5 / C9 or C9 monomer streams and polyterpene resins based on a-pinene and / or ß-pinene and / or d-limonene. These tackifier resins can be used either alone or as a mixture. In principle, both solid and liquid resins can be used at room temperature. Adhesive resins, hydrogenated or non-hydrogenated, which also contain oxygen, can optionally contain up to a maximum proportion of 25% by weight, based on the total mass of the adhesive resins contained in the polymer foam, in the polymer foam of embodiment III such as rosin and / or rosin ester resins and / or terpene phenolic resins.
Besonders bevorzugt ist das Klebharz ein nicht hydriertes Kohlenwasserstoffharz, insbesondere auf der Basis von a-Pinen. Diese Harze verleihen dem Polymerschaum neben einer hohen Kohäsion vorteilhaft auch eine sehr hohe Adhäsion, insbesondere auch bei hohen Temperaturen. The adhesive resin is particularly preferably a non-hydrogenated hydrocarbon resin, in particular based on α-pinene. In addition to high cohesion, these resins advantageously also give the polymer foam a very high level of adhesion, in particular even at high temperatures.
Bevorzugt enthält der Polymerschaum der Ausführungsform III 20 bis 60 Gew.-%, besonders bevorzugt 30 bis 50 Gew.-%, jeweils bezogen auf das Gesamtgewicht des Polymerschaums, mindestens eines Klebharzes. The polymer foam of embodiment III preferably contains 20 to 60% by weight, particularly preferably 30 to 50% by weight, based in each case on the total weight of the polymer foam, of at least one adhesive resin.
Schäumung Foaming
Grundsätzlich lassen sich Schäume auf zwei Wegen hersteilen: zum einen durch die Einwirkung eines Treibgases, sei es als solches zugesetzt oder aus einer chemischen Reaktion resultierend, zum anderen durch die Einarbeitung von Hohlkugeln in die Werkstoffmatrix. Schäume, die auf letzterem Wege hergestellt werden, werden als syntaktische Schäume bezeichnet. Basically, foams can be produced in two ways: on the one hand by the action of a propellant gas, either added as such or resulting from a chemical reaction, on the other hand by incorporating hollow spheres into the material matrix. Foams made in the latter way are known as syntactic foams.
Physikalische Treibmittel sind irgendwelche natürlich vorkommenden atmosphärischen Materialien, die bei der Temperatur und dem Druck, bei denen der Schaum aus der Düse austritt, gasförmig sind. Physikalische Treibmittel können in das Matrixmaterial als Gas, als ein überkritisches Fluid oder als eine Flüssigkeit eingeführt, d.h. injiziert werden. Die Wahl des verwendeten physikalischen Treibmittels hängt von den gewünschten Eigenschaften der resultierenden Schäume ab. Andere Faktoren, die bei der Auswahl eines Treibmittels zu berücksichtigen sind, sind seine Toxizität, das Dampfdruckprofil, die Einfachheit der Handhabung und die Löslichkeit in Bezug auf die verwendeten polymeren Materialien. Entflammbare Treibmittel wie Pentan, Butan und andere organische Materialien wie Fluorkohlenwasserstoffe und Fluorchlorkohlenwasserstoffe können verwendet werden; bevorzugt werden jedoch nicht brennbare, nicht toxische, nicht ozonabbauende Treibmittel, weil sie leichter zu verwenden sind, weniger Bedenken hinsichtlich ihrer Auswirkungen auf die Umwelt bestehen etc. Bevorzugte physikalische Treibmittel sind Kohlendioxid, Stickstoff, SF6, Stickstoffoxide, perfluorierte Flüssigkeiten wie C2F6, Edelgase wie Helium, Argon und Xenon, Luft (typischerweise eine Mischung aus Stickstoff und Sauerstoff) und Mischungen dieser Materialien. Alternativ können auch chemische Treibmittel zur Schäumung verwendet werden. Geeignete chemische Treibmittel umfassen Mischungen aus Natriumbicarbonat und Zitronensäure, Dinitrosopentamethylentetramin, p-Toluolsulfonylhydrazid, 4-4'-Oxybis (benzolsulfonyl- hydrazid, Azodicarbonamid (1 ,1'-Azobisformamid), p-Toluolsulfonylsemicarbazid, 5-Phenyltetrazol, 5 -Phenyltetrazol-Analoga, Diisopropylhydrazodicarboxylat, 5-Phenyl-3,6- dihydro-1 , 3,4-Oxadiazin-2-on und Natriumborhydrid. Physical blowing agents are any naturally occurring atmospheric material that is gaseous at the temperature and pressure at which the foam emerges from the nozzle. Physical propellants can be introduced, ie injected, into the matrix material as a gas, as a supercritical fluid or as a liquid. The choice of physical blowing agent used depends on the desired properties of the resulting foams. Other factors to consider when choosing a blowing agent are its toxicity, vapor pressure profile, ease of handling, and solubility with respect to the polymeric materials used. Flammable propellants such as pentane, butane, and other organic materials such as fluorocarbons and chlorofluorocarbons can be used; however, preference is given to non-flammable, non-toxic, non-ozone-depleting propellants because they are easier to use, there are fewer concerns about their effects on the environment, etc. Preferred physical propellants are carbon dioxide, nitrogen, SF6, nitrogen oxides, perfluorinated liquids such as C2F6, noble gases such as Helium, argon and xenon, air (typically a mixture of nitrogen and oxygen), and mixtures of these materials. Alternatively, chemical blowing agents can also be used for foaming. Suitable chemical propellants include mixtures of sodium bicarbonate and citric acid, dinitrosopentamethylenetetramine, p-toluenesulfonyl hydrazide, 4-4'-oxybis (benzenesulfonylhydrazide, azodicarbonamide (1,1'-azobisformamide), p-toluenesulfonoga-tetyl-tetrazyl-prazole, 5-phenrazyl-analogs , Diisopropyl hydrazodicarboxylate, 5-phenyl-3,6-dihydro-1, 3,4-oxadiazin-2-one and sodium borohydride.
Bevorzugt enthält die Polymerschaumschicht Mikroballons; sie ist in diesem Fall zumindest unter Einsatz von Mikroballons aufgeschäumt. Sofern sie nur mittels Mikroballons aufgeschäumt ist, ist sie ein syntaktischer Schaum. The polymer foam layer preferably contains microballoons; in this case it is at least foamed using microballoons. If it is only foamed using microballoons, it is a syntactic foam.
Unter „Mikroballons“ werden elastische und somit in ihrem Grundzustand expandierbare Mikrohohlkugeln verstanden, die eine thermoplastische Polymerhülle aufweisen. Diese Kugeln sind mit niedrigsiedenden Flüssigkeiten oder verflüssigtem Gas gefüllt. Als Hüllenmaterial finden insbesondere Polyacrylnitril, PVDC, PVC oder Polyacrylate Verwendung. Als niedrigsiedende Flüssigkeit sind insbesondere Kohlenwasserstoffe der niederen Alkane, beispielsweise Isobutan oder Isopentan gebräuchlich, die als verflüssigtes Gas unter Druck in der Polymerhülle eingeschlossen sind. “Microballoons” are understood to mean elastic and thus expandable microspheres in their basic state, which have a thermoplastic polymer shell. These balls are filled with low-boiling liquids or liquefied gas. In particular, polyacrylonitrile, PVDC, PVC or polyacrylates are used as the shell material. Hydrocarbons of the lower alkanes, for example isobutane or isopentane, which are enclosed as a liquefied gas under pressure in the polymer shell, are particularly common as the low-boiling liquid.
Durch ein Einwirken auf die Mikroballons, insbesondere durch eine Wärmeeinwirkung, erweicht die äußere Polymerhülle. Gleichzeitig geht das in der Hülle befindliche flüssige Treibgas in seinen gasförmigen Zustand über. Dabei dehnen sich die Mikroballons irreversibel aus und expandieren dreidimensional. Die Expansion ist beendet, wenn sich der Innen- und der Außendruck ausgleichen. Da die polymere Hülle erhalten bleibt, erzielt man so einen geschlossenzeiligen Schaum. By acting on the microballoons, in particular by applying heat, the outer polymer shell softens. At the same time, the liquid propellant in the envelope changes into its gaseous state. The microballoons expand irreversibly and expand three-dimensionally. The expansion is finished when the internal and external pressures equalize. Since the polymer shell is retained, a closed-cell foam is achieved.
Es ist eine Vielzahl an Mikroballontypen kommerziell erhältlich, welche sich im Wesentlichen über ihre Größe (6 bis 45 pm Durchmesser im unexpandierten Zustand) und ihre zur Expansion benötigten Starttemperaturen (75 bis 220 °C) differenzieren. Unexpandierte Mikroballontypen sind auch als wässrige Dispersion mit einem Feststoff- beziehungsweise Mikroballonanteil von ca. 40 bis 45 Gew.-% erhältlich, weiterhin auch als polymergebundene Mikroballons (Masterbatche), zum Beispiel in Ethylenvinylacetat mit einer Mikroballonkonzentration von ca. 65 Gew.-%. Sowohl die Mikroballon-Dispersionen als auch die Masterbatche sind wie die unexpandierten Mikroballons als solche zur Herstellung der Polymerschaumschicht geeignet. A large number of types of microballoons are commercially available, which differ essentially in terms of their size (6 to 45 μm diameter in the unexpanded state) and their starting temperatures (75 to 220 ° C.) required for expansion. Unexpanded types of microballoons are also available as aqueous dispersions with a solids or microballoon content of approx. 40 to 45% by weight, and also as polymer-bound microballoons (masterbatches), for example in ethylene vinyl acetate with a microballoon concentration of approx. 65% by weight. Both the microballoon dispersions and the masterbatches, like the unexpanded microballoons, are suitable as such for producing the polymer foam layer.
Der Polymerschaum kann auch mit sogenannten vorexpandierten Mikroballons erzeugt werden. Bei dieser Gruppe findet die Expansion schon vor der Einmischung in die Polymermatrix statt. Die Polymerschäume können auch mit geschäumten Partikeln erzeugt werden, also mit expandierten oder expandierbaren Kügelchen aus insbesondere Polystyrol, Polypropylen, thermoplastischem Polyurethan oder Celluloseacetat, für die sich im Englischen die Bezeichnung „beads“ durchgesetzt hat. Es werden also Partikel aus an sich schon aufgeschäumten Kunststoffen in die Polymermatrix eingemischt, welche die Dichteerniedrigung bewirken. Die Partikel können auch ungeschäumt in die Polymermatrix gegeben und erst dann aufgeschäumt werden. Ferner kann der Polymerschaum auch aus thermisch miteinander verbundenen, insbesondere verschweißten, ggf. vorexpandierten „beads“ bestehen, so dass in diesem Fall keine weitere umgebende Matrix vorhanden ist.The polymer foam can also be produced with so-called pre-expanded microballoons. In this group, expansion takes place before it is mixed into the polymer matrix. The polymer foams can also be produced with foamed particles, that is to say with expanded or expandable beads made of, in particular, polystyrene, polypropylene, thermoplastic polyurethane or cellulose acetate, for which the term “beads” has become established. Particles of already foamed plastics are mixed into the polymer matrix, which cause the density to decrease. The particles can also be placed in the polymer matrix without being foamed and only then foamed. Furthermore, the polymer foam can also consist of “beads” thermally connected to one another, in particular welded, possibly pre-expanded, so that in this case no further surrounding matrix is present.
Der Polymerschaum kann Alterungsschutzmittel enthalten, z.B. primäre Antioxidantien wie sterisch gehinderte Phenole, sekundäre Antioxidantien wie Phosphite oder Thioether und/oder C-Radikalfänger. Weiter können z.B. Lichtschutzmittel wie UV-Absorber oder sterisch gehinderte Amine; Antiozonantien; Metalldeaktivatoren und/oder Verarbeitungshilfsmittel enthalten sein. The polymer foam can contain anti-aging agents, e.g. primary antioxidants such as sterically hindered phenols, secondary antioxidants such as phosphites or thioethers and / or carbon radical scavengers. It is also possible, for example, to use light stabilizers such as UV absorbers or sterically hindered amines; Antiozonants; Metal deactivators and / or processing aids may be included.
Weiter kann der Polymerschaum Füllstoffe wie zum Beispiel Siliziumdioxid, Glas (gemahlen oder in Form von Kugeln), Aluminiumoxide, Zinkoxide, Calciumcarbonate, Titandioxide, Ruße, etc. enthalten, ebenso Pigmente, Farbstoffe und/oder optische Aufheller. The polymer foam can also contain fillers such as silicon dioxide, glass (ground or in the form of spheres), aluminum oxides, zinc oxides, calcium carbonates, titanium dioxide, carbon blacks, etc., as well as pigments, dyes and / or optical brighteners.
Außere Haftklebmasseschicht Outer pressure sensitive adhesive layer
Unter einer Haftklebmasse bzw. einem Haftklebstoff wird erfindungsgemäß, wie im allgemeinen Sprachgebrauch üblich, ein Stoff verstanden, der zumindest bei Raumtemperatur dauerhaft klebrig sowie klebfähig ist. Charakteristisch für einen Haftklebstoff ist, dass er durch Druck auf ein Substrat aufgebracht werden kann und dort haften bleibt, wobei der aufzuwendende Druck und die Einwirkdauer dieses Drucks nicht näher definiert werden. Im allgemeinen, grundsätzlich jedoch abhängig von der genauen Art des Haftklebstoffs sowie des Substrats, der Temperatur und der Luftfeuchtigkeit, reicht die Einwirkung eines kurzfristigen, minimalen Drucks, der über eine leichte Berührung für einen kurzen Moment nicht hinausgeht, um den Haftungseffekt zu erzielen, in anderen Fällen kann auch eine längerfristige Einwirkdauer eines höheren Drucks notwendig sein. According to the invention, a pressure-sensitive adhesive or a pressure-sensitive adhesive is understood, as is customary in common parlance, to be a substance which is permanently tacky and also tacky at least at room temperature. It is characteristic of a pressure-sensitive adhesive that it can be applied to a substrate by pressure and remains adhered there, the pressure to be applied and the duration of this pressure not being defined in more detail. In general, but basically depending on the exact type of pressure-sensitive adhesive as well as the substrate, the temperature and the air humidity, the application of a short-term, minimal pressure, which does not go beyond a light touch for a short moment, is sufficient to achieve the adhesive effect in other cases a longer period of exposure to a higher pressure may be necessary.
Haftklebmassen haben besondere, charakteristische viskoelastische Eigenschaften, die zu der dauerhaften Klebrigkeit und Klebfähigkeit führen. Kennzeichnend für sie ist, dass, wenn sie mechanisch deformiert werden, es sowohl zu viskosen Fließprozessen als auch zum Aufbau elastischer Rückstellkräfte kommt. Beide Prozesse stehen hinsichtlich ihres jeweiligen Anteils in einem bestimmten Verhältnis zueinander, abhängig sowohl von der genauen Zusammensetzung, der Struktur und dem Vernetzungsgrad der Haftklebemasse als auch von der Geschwindigkeit und Dauer der Deformation sowie von der Temperatur. Pressure-sensitive adhesives have special, characteristic viscoelastic properties which lead to permanent tack and adhesiveness. They are characterized by the fact that when they are mechanically deformed, both viscous flow processes and the build-up of elastic restoring forces occur. Both processes are related to each other in terms of their respective share, depending on the exact one Composition, the structure and the degree of crosslinking of the PSA as well as the speed and duration of the deformation and the temperature.
Der anteilige viskose Fluss ist zur Erzielung von Adhäsion notwendig. Nur die viskosen Anteile, häufig hervorgerufen durch Makromoleküle mit relativ großer Beweglichkeit, ermöglichen eine gute Benetzung und ein gutes Auffließen auf das zu verklebende Substrat. Ein hoher Anteil an viskosem Fluss führt zu einer hohen Haftklebrigkeit (auch als Tack oder Oberflächenklebrigkeit bezeichnet) und damit oft auch zu einer hohen Adhäsion. Stark vernetzte Systeme, kristalline oder glasartig erstarrte Polymere sind mangels fließfähiger Anteile in der Regel nicht oder zumindest nur wenig haftklebrig. The proportionate viscous flow is necessary to achieve adhesion. Only the viscous components, often caused by macromolecules with relatively high mobility, enable good wetting and flow onto the substrate to be bonded. A high proportion of viscous flow leads to high pressure-sensitive tack (also referred to as tack or surface tack) and thus often also to high adhesion. Strongly cross-linked systems, crystalline or glass-like solidified polymers are generally not or at least only slightly tacky due to the lack of flowable components.
Die anteiligen elastischen Rückstellkräfte sind zur Erzielung von Kohäsion notwendig. Sie werden zum Beispiel durch sehr langkettige und stark verknäuelte sowie durch physikalisch oder chemisch vernetzte Makromoleküle hervorgerufen und ermöglichen die Übertragung der auf eine Klebverbindung angreifenden Kräfte. Sie führen dazu, dass eine Klebverbindung einer auf sie einwirkenden Dauerbelastung, zum Beispiel in Form einer dauerhaften Scherbelastung, in ausreichendem Maße über einen längeren Zeitraum standhalten kann.The proportional elastic restoring forces are necessary to achieve cohesion. They are caused, for example, by very long-chain and strongly tangled macromolecules as well as by physically or chemically cross-linked macromolecules and enable the forces acting on an adhesive bond to be transmitted. They lead to the fact that an adhesive connection can withstand a permanent load acting on it, for example in the form of permanent shear stress, to a sufficient extent over a longer period of time.
Zur genaueren Beschreibung und Quantifizierung des Maßes an elastischem und viskosem Anteil sowie des Verhältnisses der Anteile zueinander werden die mittels Dynamisch Mechanischer Analyse (DMA) ermittelbaren Größen Speichermodul (G‘) und Verlustmodul (G“) herangezogen. G‘ ist ein Maß für den elastischen Anteil, G“ ein Maß für den viskosen Anteil eines Stoffes. Beide Größen sind abhängig von der Deformationsfrequenz und der Temperatur. The storage modulus (G ‘) and loss modulus (G”) that can be determined by means of dynamic mechanical analysis (DMA) are used for a more precise description and quantification of the amount of elastic and viscous components as well as the relationship between the components. G ‘is a measure for the elastic part, G“ is a measure for the viscous part of a substance. Both sizes are dependent on the deformation frequency and the temperature.
Die Größen können mit Hilfe eines Rheometers ermittelt werden. Das zu untersuchende Material wird dabei zum Beispiel in einer Platte-Platte-Anordnung einer sinusförmig oszil lierenden Scherbeanspruchung ausgesetzt. Bei schubspannungsgesteuerten Geräten werden die Deformation als Funktion der Zeit und der zeitliche Versatz dieser Deformation gegenüber dem Einbringen der Schubspannung gemessen. Dieser zeitliche Versatz wird als Phasenwinkel d bezeichnet. The sizes can be determined with the aid of a rheometer. The material to be examined is exposed to a sinusoidal oscillating shear stress, for example in a plate-plate arrangement. In devices controlled by shear stress, the deformation is measured as a function of time and the time offset of this deformation with respect to the introduction of the shear stress. This time offset is referred to as the phase angle d.
Der Speichermodul G‘ ist wie folgt definiert: G' = (t/g) *cos(ö) (T = Schubspannung, y = Deformation, d = Phasenwinkel = Phasenverschiebung zwischen Schubspannungs- und Deformationsvektor). Die Definition des Verlustmoduls G" lautet: G" = (t/g) · sin(ö) (T = Schubspannung, g = Deformation, d = Phasenwinkel = Phasenverschiebung zwischen Schubspannungs- und Deformationsvektor). The storage modulus G 'is defined as follows: G' = (t / g) * cos (δ) (T = shear stress, y = deformation, d = phase angle = phase shift between shear stress and deformation vector). The definition of the loss modulus G "is: G" = (t / g) · sin (δ) (T = shear stress, g = deformation, d = phase angle = phase shift between shear stress and deformation vector).
Eine Masse gilt insbesondere dann als Haftklebmasse und wird im Sinne der Erfindung insbesondere dann als solche definiert, wenn bei 23 °C im Deformationsfrequenzbereich von 10° bis 101 rad/sec sowohl G‘ als auch G“ zumindest zum Teil im Bereich von 103 bis 107 Pa liegen. „Zum Teil“ heißt, dass zumindest ein Abschnitt der G‘-Kurve innerhalb des Fensters liegt, das durch den Deformationsfrequenzbereich von einschließlich 10° bis einschließlich 101 rad/sec (Abszisse) sowie den Bereich der G‘-Werte von einschließlich 103 bis einschließlich 107 Pa (Ordinate) aufgespannt wird, und wenn zumindest ein Abschnitt der G“-Kurve ebenfalls innerhalb des entsprechenden Fensters liegt. In particular, a mass is considered a pressure-sensitive adhesive and is defined as such within the meaning of the invention if at 23 ° C in the deformation frequency range of 10 ° to 10 1 rad / sec both G 'and G ″ are at least partially in the range of 10 3 up to 10 7 Pa lie. “Partly” means that at least a section of the G 'curve lies within the window that is defined by the deformation frequency range from 10 ° up to and including 10 1 rad / sec (abscissa) and the range of G' values from 10 3 inclusive up to and including 10 7 Pa (ordinate), and if at least a section of the G “curve is also within the corresponding window.
Die äußere Haftklebmasseschicht enthält bevorzugt zu mindestens 50 Gew.-%, stärker bevorzugt zu mindestens 70 Gew.-%, besonders bevorzugt zu mindestens 90 Gew.-%, insbesondere zu mindestens 95 Gew.-%, beispielsweise zu mindestens 97 Gew.-%, jeweils bezogen auf das Gesamtgewicht der Haftklebemasseschicht, ein oder mehrereThe outer pressure-sensitive adhesive layer preferably contains at least 50% by weight, more preferably at least 70% by weight, particularly preferably at least 90% by weight, in particular at least 95% by weight, for example at least 97% by weight , in each case based on the total weight of the pressure-sensitive adhesive layer, one or more
Poly(meth)acrylat(e). Poly (meth) acrylate (s).
Besonders bevorzugt enthält die äußere Haftklebmasseschicht zu mindestens 50 Gew.-%, stärker bevorzugt zu mindestens 70 Gew.-%, besonders bevorzugt zu mindestens 90 Gew.- %, insbesondere zu mindestens 95 Gew.-%, beispielsweise zu mindestens 97 Gew.-%, jeweils bezogen auf das Gesamtgewicht der Haftklebemasseschicht, ein oder mehrereThe outer pressure-sensitive adhesive layer particularly preferably contains at least 50% by weight, more preferably at least 70% by weight, particularly preferably at least 90% by weight, in particular at least 95% by weight, for example at least 97% by weight %, in each case based on the total weight of the pressure-sensitive adhesive layer, one or more
Poly(meth)acrylat(e), die auf die folgende Monomerenzusammensetzung zurückzuführen sind: Poly (meth) acrylate (s), which can be traced back to the following monomer composition:
Moni ) mindestens ein Acrylsäureester und/oder Methacrylsäureester der Formel (2) Moni) at least one acrylic acid ester and / or methacrylic acid ester of the formula (2)
CH2=C(RIM)(COORiv) (2), worin Rm = H oder CH3 und RIV ein Alkylrest mit 4 bis 12 C-Atomen ist; CH 2 = C (R IM ) (COOR iv ) (2), in which R m = H or CH 3 and R IV is an alkyl radical having 4 to 12 carbon atoms;
Mon2) mindestens ein olefinisch ungesättigtes Monomer mit mindestens einer funktionellen Gruppe ausgewählt aus der Gruppe bestehend aus Carbonsäuregruppen, Sulfonsäuregruppen, Phosphonsäuregruppen, Hydroxygruppen,Mon2) at least one olefinically unsaturated monomer with at least one functional group selected from the group consisting of carboxylic acid groups, sulfonic acid groups, phosphonic acid groups, hydroxyl groups,
Säureanhydridgruppen, Epoxidgruppen und Aminogruppen Acid anhydride groups, epoxy groups and amino groups
Mon3) optional mindestens ein Acrylsäureester und/oder Methacrylsäureester der Formel (3) Mon3) optionally at least one acrylic acid ester and / or methacrylic acid ester of the formula (3)
CH2=C(RV)(COORvi) (3), worin Rv = H oder CH3 und RVI ein Alkylrest mit 1 bis 3 C-Atomen ist. CH 2 = C (R V ) (COOR vi ) (3), in which R v = H or CH3 and R VI is an alkyl radical having 1 to 3 carbon atoms.
Es können unabhängig voneinander jeweils ein oder mehrere Monomere Moni , Mon2 und Mon3 in der Monomerenzusammensetzung enthalten sein. The monomer composition can contain one or more monomers Moni, Mon2 and Mon3, independently of one another.
Monomere Moni sind dabei bevorzugt zu mindestens 70 Gew.-%, stärker bevorzugt zu mindestens 80 Gew.-%, jeweils bezogen auf das Gesamtgewicht derMonomeric moni are preferably at least 70% by weight, more preferably at least 80% by weight, based in each case on the total weight of the
Monomerenzusammensetzung, in dieser enthalten. Monomere Mon2 sind bevorzugt zu 1 bis 15 Gew.-%, bezogen auf das Gesamtgewicht der Monomerenzusammensetzung, in dieser enthalten. Monomer composition contained in this. Monomeric Mon2 are preferably contained in the monomer composition in an amount of 1 to 15% by weight, based on the total weight of the latter.
Monomere Mon3 sind, sofern überhaupt enthalten, bevorzugt zu 5 bis 15 Gew.-%, bezogen auf das Gesamtgewicht der Monomerenzusammensetzung, in dieser enthalten. Monomeric Mon3, if present at all, is preferably present in an amount of 5 to 15% by weight, based on the total weight of the monomer composition.
Die Monomere Moni umfassen bevorzugt mindestens ein verzweigtes Monomer. Besonders bevorzugt sind die Monomere a) ausgewählt aus der Gruppe bestehend aus n-Butylacrylat, n- Butylmethacrylat, n-Pentylacrylat, n-Pentylmethacrylat, n-Amylacrylat, n-Hexylacrylat, n- Hexylmethacrylat, n-Heptylacrylat, n-Octylacrylat, n-Octylmethacrylat, n-Nonylacrylat, Isobutylacrylat, Isooctylacrylat, Isooctylmethacrylat, 2-Ethylhexylacrylat und 2-Ethylhexylmethacrylat, 2-Propylheptylacrylat und Isobornylacrylat. Besonders bevorzugt sind die Monomere Moni ausgewählt aus n-Butylacrylat, 2-Ethylhexylacrylat und Isobornylacrylat. The monomers moni preferably comprise at least one branched monomer. Particularly preferred are the monomers a) selected from the group consisting of n-butyl acrylate, n-butyl methacrylate, n-pentyl acrylate, n-pentyl methacrylate, n-amyl acrylate, n-hexyl acrylate, n-hexyl methacrylate, n-heptyl acrylate, n-octyl acrylate, n -Octyl methacrylate, n-nonylacrylate, isobutyl acrylate, isooctyl acrylate, isooctyl methacrylate, 2-ethylhexyl acrylate and 2-ethylhexyl methacrylate, 2-propylheptyl acrylate and isobornyl acrylate. The monomers Moni are particularly preferably selected from n-butyl acrylate, 2-ethylhexyl acrylate and isobornyl acrylate.
Die Monomere Mon2 sind bevorzugt ausgewählt aus der Gruppe bestehend aus Acrylsäure, Methacrylsäure, Itaconsäure, Maleinsäure, Fumarsäure, Crotonsäure, Aconitsäure, Dimethylacrylsäure, ß-Acryloyloxypropionsäure, Trichloracrylsäure, Vinylessigsäure, Vinylphosphonsäure, Maleinsäureanhydrid, Hydroxyethylacrylat, Hydroxypropylacrylat, Hydroxyethylmethacrylat, Hydroxypropylmethacrylat, 6-Hydroxyhexylmethacrylat, Allylalkohol, Glycidylacrylat und Glycidylmethacrylat. Besonders bevorzugt ist als Monomer Mon2 Acrylsäure enthalten. The monomers Mon2 are preferably selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, aconitic acid, dimethylacrylic acid, β-acryloyloxypropionic acid, trichloroacrylic acid, vinyl acetic acid, vinylphosphonic acid, maleic anhydride, hydroxyhexyl acrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxyhexyl acrylate, hydroxypropyl acrylate, hydroxyhexyl acrylate, hydroxypropyl acrylate, hydroxyhexyl acrylate, hydroxypropyl methacrylate, fumaric acid, crotonic acid, fumaric acid, hydroxyethyl acrylate, hydroxypropyl methacrylate, hydroxyhexyl acrylate, hydroxypropyl methacrylate, hydroxyhexyl acrylate, hydroxypropyl methacrylate, maleic acid, fumaric acid, crotonic acid, fumaric acid, crotonic acid , Allyl alcohol, glycidyl acrylate and glycidyl methacrylate. Acrylic acid is particularly preferred as monomer Mon2.
Als Monomer Mon3 ist, sofern überhaupt enthalten, bevorzugt Methylacrylat enthalten. The monomer Mon3, if present at all, is preferably methyl acrylate.
Besonders bevorzugt ist das Poly(meth)acrylat der äußeren Haftklebmasseschicht auf eine Monomerenzusammensetzung umfassend The poly (meth) acrylate of the outer pressure-sensitive adhesive layer on a monomer composition is particularly preferred
70 bis 95 Gew.-% 2-Ethylhexylacrylat, n-Butylacrylat und/oder Isobornylacrylat; insbesondere n-Butylacrylat und 2-Ethylhexylacrylat; 70 to 95% by weight of 2-ethylhexyl acrylate, n-butyl acrylate and / or isobornyl acrylate; in particular n-butyl acrylate and 2-ethylhexyl acrylate;
1 bis 15 Gew.-% Acrylsäure; und 1 to 15% by weight acrylic acid; and
0 bis 15 Gew.-% Methylacrylat zurückzuführen. 0 to 15 wt .-% methyl acrylate returned.
Insbesondere ist das Poly(meth)acrylat der äußeren Haftklebmasseschicht auf eine Monomerenzusammensetzung bestehend aus In particular, the poly (meth) acrylate of the outer pressure-sensitive adhesive layer is composed of a monomer composition
70 bis 95 Gew.-% 2-Ethylhexylacrylat, n-Butylacrylat und/oder Isobornylacrylat; insbesondere n-Butylacrylat und 2-Ethylhexylacrylat; 70 to 95% by weight of 2-ethylhexyl acrylate, n-butyl acrylate and / or isobornyl acrylate; in particular n-butyl acrylate and 2-ethylhexyl acrylate;
1 bis 15 Gew.-% Acrylsäure; und 0 bis 15 Gew.-% Methylacrylat zurückzuführen. 1 to 15% by weight acrylic acid; and 0 to 15 wt .-% methyl acrylate returned.
Die Poly(meth)acrylate der äußeren Haftklebmasseschicht sind bevorzugt thermisch, insbesondere kovalent und/oder koordinativ vernetzt. Bevorzugte kovalente Vernetzer Epoxyverbindungen, bevorzugte koordinative Vernetzer sind Aluminiumchelate. The poly (meth) acrylates of the outer pressure-sensitive adhesive layer are preferably crosslinked thermally, in particular covalently and / or coordinatively. Preferred covalent crosslinking agents are epoxy compounds, preferred coordinative crosslinking agents are aluminum chelates.
Das gewichtsmittlere Molekulargewicht Mw der Poly(meth)acrylate der äußeren Haftklebmasseschicht beträgt bevorzugt 20.000 bis 2.000.000 g/mol, besonders bevorzugt 100.000 bis 1.500.000 g/mol, insbesondere 200.000 bis 1.200.000 g/mol. Die Angaben des mittleren Molekulargewichtes Mw in dieser Schrift beziehen sich auf die Bestimmung per Gelpermeationschromatographie (siehe experimenteller Teil). The weight-average molecular weight M w of the poly (meth) acrylates of the outer pressure-sensitive adhesive layer is preferably from 20,000 to 2,000,000 g / mol, particularly preferably from 100,000 to 1,500,000 g / mol, in particular from 200,000 to 1,200,000 g / mol. The information on the average molecular weight M w in this document relates to the determination by gel permeation chromatography (see experimental section).
Außere thermoplastische Folie Outer thermoplastic film
„Äußere thermoplastische Folie“ bedeutet, dass die thermoplastische Folie nach außen weist und somit den Aufbau des Klebebandes auf ihrer Seite abschließt. “Outer thermoplastic film” means that the thermoplastic film faces outwards and thus completes the structure of the adhesive tape on its side.
Eine thermoplastische Folie weist keine oder nur sehr gering ausgeprägte Klebeigenschaften auf, so dass sie in jedem denkbaren Aufbau des erfindungsgemäßen Klebebands, der eine äußere thermoplastische Folie umfasst, die Seite mit der schwächeren Klebkraft abschließt. Sofern das Klebeband also eine äußere thermoplastische Folie umfasst, weist es auf seiner mit der äußeren thermoplastischen Folie ausgestatteten Seite eine niedrigere Klebkraft auf als auf der gegenüberliegenden Seite oder es weist auf seiner mit der äußeren thermoplastischen Folie ausgestatteten Seite keine Klebkraft auf. A thermoplastic film has little or no adhesive properties, so that in every conceivable structure of the adhesive tape according to the invention, which comprises an outer thermoplastic film, it closes the side with the weaker bond strength. If the adhesive tape thus comprises an outer thermoplastic film, it has a lower bond strength on its side equipped with the outer thermoplastic film than on the opposite side, or it has no bond strength on its side equipped with the outer thermoplastic film.
Bevorzugt umfasst die thermoplastische Folie mindestens ein Polymer ausgewählt aus der Gruppe bestehend aus thermoplastischen Polyolefinen (TPE-E bzw. TPO), insbesondere thermoplastischen Polyolefinelastomeren (POE) und thermoplastischen Polyolefinplastomeren (POP); thermoplastischen Polystyrolelastomeren (TPE-S bzw. TPS), insbesondere Styrolblockcopolymeren (SBC); thermoplastischen Polyurethanelastomeren (TPE-U bzw. TPU); thermoplastischen Polyesterelastomeren und Copolyestern (TPE-E bzw. TPC); thermoplastischen Copolyamiden (TPE-A bzw. TPA); und thermoplastischen Vulkanisaten sowie vernetzten thermoplastischen Polyolefinelastomeren (TPE-V bzw. TPV).The thermoplastic film preferably comprises at least one polymer selected from the group consisting of thermoplastic polyolefins (TPE-E or TPO), in particular thermoplastic polyolefin elastomers (POE) and thermoplastic polyolefin plastomers (POP); thermoplastic polystyrene elastomers (TPE-S or TPS), in particular styrene block copolymers (SBC); thermoplastic polyurethane elastomers (TPE-U or TPU); thermoplastic polyester elastomers and copolyesters (TPE-E or TPC); thermoplastic copolyamides (TPE-A or TPA); and thermoplastic vulcanizates as well as cross-linked thermoplastic polyolefin elastomers (TPE-V or TPV).
Insbesondere besteht die thermoplastische Folie aus mindestens einem, besonders bevorzugt einem, Polymer ausgewählt aus der Gruppe bestehend aus thermoplastischen Polyolefinen (TPE-E bzw. TPO), insbesondere thermoplastischen Polyolefinelastomeren (POE) und thermoplastischen Polyolefinplastomeren (POP); thermoplastischen Polystyrolelastomeren (TPE-S bzw. TPS), insbesondere Styrolblockcopolymeren (SBC); thermoplastischen Polyurethanelastomeren (TPE-U bzw. TPU); thermoplastischen Polyesterelastomeren und Copolyestern (TPE-E bzw. TPC); thermoplastischen Copolyamiden (TPE-A bzw. TPA); und thermoplastischen Vulkanisaten sowie vernetzten thermoplastischen Polyolefinelastomeren (TPE-V bzw. TPV). In particular, the thermoplastic film consists of at least one, particularly preferably one, polymer selected from the group consisting of thermoplastic polyolefins (TPE-E or TPO), in particular thermoplastic polyolefin elastomers (POE) and thermoplastic polyolefin elastomers (POP); thermoplastic polystyrene elastomers (TPE-S or TPS), in particular styrene block copolymers (SBC); thermoplastic polyurethane elastomers (TPE-U or TPU); thermoplastic polyester elastomers and copolyesters (TPE-E or TPC); thermoplastic copolyamides (TPE-A or TPA); and thermoplastic vulcanizates as well as cross-linked thermoplastic polyolefin elastomers (TPE-V or TPV).
Klebebandaufbau Tape construction
Der Aufbau bzw. die Schichtabfolge eines erfindungsgemäßen Klebebandes umfasst mehrere Varianten. In einer Ausführungsform beschränkt sich der Aufbau des erfindungsgemäßen Klebebandes auf die Polymerschaumschicht und eine äußere Haftklebmasseschicht. In diesem Fall besteht das erfindungsgemäße Klebeband somit aus a) einer Polymerschaumschicht und b) einer äußeren Haftklebmasseschicht. The structure or the layer sequence of an adhesive tape according to the invention comprises several variants. In one embodiment, the structure of the adhesive tape of the invention is limited to the polymer foam layer and an outer pressure-sensitive adhesive layer. In this case, the adhesive tape of the invention thus consists of a) a polymer foam layer and b) an outer pressure-sensitive adhesive layer.
Die erforderliche schwächere Klebkraft auf der der äußeren Haftklebmasseschicht gegenüberliegenden Seite resultiert in diesem Fall daraus, dass die freiliegende Seite der Polymerschaumschicht eine schwächere Klebkraft aufweist als die Haftklebmasseschicht. Bevorzugt entspricht in dieser Ausführungsform die Polymerschaumschicht einer Polymerschaumschicht der dort beschriebenen Ausführungsform II; die Polymerschaumschicht, insbesondere das Matrixmaterial der Polymerschaumschicht, enthält also bevorzugt mindestens ein Poly(meth)acrylat. Alle näheren, im Rahmen der Ausführungsform II der Polymerschaumschicht beschriebenen Ausgestaltungen gelten hier entsprechend. The required weaker bond strength on the side opposite the outer PSA layer results in this case from the fact that the exposed side of the polymer foam layer has a weaker bond strength than the PSA layer. In this embodiment, the polymer foam layer preferably corresponds to a polymer foam layer of embodiment II described there; the polymer foam layer, in particular the matrix material of the polymer foam layer, therefore preferably contains at least one poly (meth) acrylate. All the more detailed configurations described in the context of embodiment II of the polymer foam layer apply here accordingly.
Grundsätzlich umfasst die Erfindung auch eine Ausführungsform, in der auf beiden Seiten der Polymerschaumschicht jeweils eine äußere Haftklebmasseschicht angeordnet ist. Selbstverständlich sind, dem Grundgedanken der Erfindung folgend, die beiden äußeren Haftklebmasseschichten in diesem Fall nicht identisch und unterscheiden sich insbesondere hinsichtlich ihrer Klebkraft. In principle, the invention also comprises an embodiment in which an outer pressure-sensitive adhesive layer is arranged on each side of the polymer foam layer. Of course, following the basic idea of the invention, the two outer pressure-sensitive adhesive layers are not identical in this case and differ in particular with regard to their bond strength.
In einer weiteren Ausführungsform der Erfindung besteht das erfindungsgemäße Klebeband aus a) einer Polymerschaumschicht und b) einer äußeren thermoplastischen Folie. In a further embodiment of the invention, the adhesive tape of the invention consists of a) a polymer foam layer and b) an outer thermoplastic film.
In dieser Ausführungsform entspricht die Polymerschaumschicht bevorzugt einer Polymerschaumschicht der dort beschriebenen Ausführungsform III; die Polymerschaumschicht, insbesondere das Matrixmaterial der Polymerschaumschicht, enthält also bevorzugt mindestens ein Vinylaromatenblockcopolymer. Alle näheren, im Rahmen der Ausführungsform III der Polymerschaumschicht beschriebenen Ausgestaltungen gelten hier entsprechend. In this embodiment, the polymer foam layer preferably corresponds to a polymer foam layer of embodiment III described there; the The polymer foam layer, in particular the matrix material of the polymer foam layer, therefore preferably contains at least one vinyl aromatic block copolymer. All the more detailed configurations described in the context of embodiment III of the polymer foam layer apply here accordingly.
Die Polymerschaumschicht ist in dieser Ausführungsform insbesondere hinreichend (haft)klebrig, um einen hinreichend festen Schichtverbund zwischen sich und der äußeren thermoplastischen Folie zu ermöglichen. In this embodiment, the polymer foam layer is in particular sufficiently (adhesive) tacky to enable a sufficiently strong layer bond between itself and the outer thermoplastic film.
In einer weiteren Ausführungsform der Erfindung besteht das Klebeband aus a) einer Polymerschaumschicht; b1 ) einer äußeren Haftklebmasseschicht auf einer Seite der Polymerschaumschicht und b2) einer äußeren thermoplastischen Folie auf der der äußeren Haftklebmasseschicht gegenüberliegenden Seite der Polymerschaumschicht. In a further embodiment of the invention, the adhesive tape consists of a) a polymer foam layer; b1) an outer pressure-sensitive adhesive layer on one side of the polymer foam layer and b2) an outer thermoplastic film on the side of the polymer foam layer opposite the outer pressure-sensitive adhesive layer.
In dieser Ausführungsform entspricht die Polymerschaumschicht bevorzugt einer Polymerschaumschicht der dort beschriebenen Ausführungsform II; die Polymerschaumschicht, insbesondere das Matrixmaterial der Polymerschaumschicht, enthält also bevorzugt mindestens ein Poly(meth)acrylat. Alle näheren, im Rahmen der Ausführungsform II der Polymerschaumschicht beschriebenen Ausgestaltungen gelten hier entsprechend. In this embodiment, the polymer foam layer preferably corresponds to a polymer foam layer of embodiment II described there; the polymer foam layer, in particular the matrix material of the polymer foam layer, therefore preferably contains at least one poly (meth) acrylate. All the more detailed configurations described in the context of embodiment II of the polymer foam layer apply here accordingly.
Die Polymerschaumschicht ist in dieser Ausführungsform insbesondere hinreichend (haft)klebrig, um einen hinreichend festen Schichtverbund zwischen sich und der äußeren thermoplastischen Folie zu ermöglichen. In this embodiment, the polymer foam layer is in particular sufficiently (adhesive) tacky to enable a sufficiently strong layer bond between itself and the outer thermoplastic film.
In einer weiteren Ausführungsform umfasst das Klebeband neben der Polymerschaumschicht b1 ) eine äußere Haftklebmasseschicht auf einer Seite der Polymerschaumschicht; b2) eine äußere thermoplastische Folie auf der der äußeren Haftklebmasseschicht gegenüberliegenden Seite der Polymerschaumschicht; und c) eine weitere Haftklebmasseschicht auf der der äußeren Haftklebmasseschicht gegenüberliegenden Seite der Polymerschaumschicht. In a further embodiment, the adhesive tape comprises, in addition to the polymer foam layer b1), an outer pressure-sensitive adhesive layer on one side of the polymer foam layer; b2) an outer thermoplastic film on the side of the polymer foam layer opposite the outer pressure-sensitive adhesive layer; and c) a further pressure-sensitive adhesive layer on the side of the polymer foam layer opposite the outer pressure-sensitive adhesive layer.
Die weitere Haftklebmasseschicht befindet sich in dieser Ausführungsform somit zwischen der Polymerschaumschicht und der äußeren thermoplastischen Folie; bevorzugt verbindet sie die Polymerschaumschicht mit der äußeren thermoplastischen Folie. In this embodiment, the further pressure-sensitive adhesive layer is thus located between the polymer foam layer and the outer thermoplastic film; it preferably connects the polymer foam layer with the outer thermoplastic film.
Für die weitere Haftklebmasseschicht gilt das bei den Ausführungen zur äußeren Haftklebmasseschicht Gesagte. Bevorzugt sind die weitere Haftklebmasseschicht und die äußere Haftklebmasseschicht in Bezug auf ihre Zusammensetzung identisch; insbesondere sind sie sowohl in Bezug auf ihre Zusammensetzung als auch in Bezug auf ihre Schichtdicke identisch. The statements made in relation to the outer pressure-sensitive adhesive layer apply to the further pressure-sensitive adhesive layer. The further pressure-sensitive adhesive layer and the the outer pressure-sensitive adhesive layer is identical in terms of its composition; in particular, they are identical both in terms of their composition and in terms of their layer thickness.
Auch in dieser Ausführungsform entspricht die Polymerschaumschicht bevorzugt einer Polymerschaumschicht der dort beschriebenen Ausführungsform II; die Polymerschaumschicht, insbesondere das Matrixmaterial der Polymerschaumschicht, enthält also bevorzugt mindestens ein Poly(meth)acrylat. Alle näheren, im Rahmen der Ausführungsform II der Polymerschaumschicht beschriebenen Ausgestaltungen gelten hier entsprechend. In this embodiment too, the polymer foam layer preferably corresponds to a polymer foam layer of embodiment II described there; the polymer foam layer, in particular the matrix material of the polymer foam layer, therefore preferably contains at least one poly (meth) acrylate. All the more detailed configurations described in the context of embodiment II of the polymer foam layer apply here accordingly.
Verwendung use
Ein weiterer Gegenstand der Erfindung ist die Verwendung eines erfindungsgemäßen Klebebandes zum Abdichten einer Verbindung zwischen zwei Bauteilen. Vorteilhaft erlaubt das erfindungsgemäße Klebeband dabei ein schnelles Verkleben und somit die schnelle Herstellung der Abdichtung ohne Verrutschen und ohne die Notwendigkeit einer Aushärtung. Es können wasserdichte und wenig korrosionsanfällige Abdichtungen zur Verfügung gestellt werden. Zudem wird eine vereinfachte Demontage der Verbindung möglich, indem sich das mit der schwächer klebenden Seite verbundene Bauteil leicht entfernen lässt. Another object of the invention is the use of an adhesive tape according to the invention for sealing a connection between two components. The adhesive tape according to the invention advantageously allows rapid gluing and thus rapid production of the seal without slipping and without the need for curing. Waterproof and less susceptible to corrosion seals can be provided. In addition, a simplified dismantling of the connection is possible, in that the component connected to the weaker adhesive side can be easily removed.
Bevorzugt ist die Verbindung zwischen den beiden Bauteilen zunächst auf andere Art und Weise als durch Kleben bewirkt worden, besonders bevorzugt ist die Verbindung zwischen den Bauteilen eine mechanisch, beispielsweise Verschrauben, bewirkte Verbindung. Preferably, the connection between the two components is initially effected in a different manner than by gluing; the connection between the components is particularly preferably a mechanical connection, for example a screw connection.
Die beiden Bauteile sind grundsätzlich beliebig, der Begriff „Bauteile“ wird in einem sehr weitreichenden Sinne verstanden. Bevorzugt sind die beiden Bauteile das Gehäuse und der Deckel einer Fahrzeugbatterie; besonders bevorzugt weist beim Abdichten einer solchen Verbindung die schwächer klebende Seite des Klebebandes zum Deckel. Ferner können die Bauteile auch zu einem elektronischen Gerät, z.B. zu einem Smartphone o.ä. gehören. The two components are basically arbitrary, the term “components” is understood in a very broad sense. The two components are preferably the housing and the cover of a vehicle battery; particularly preferably, when such a connection is sealed, the weaker adhesive side of the adhesive tape faces the cover. Furthermore, the components can also belong to an electronic device, e.g. a smartphone or the like.
Ebenfalls bevorzugt wird das erfindungsgemäße Klebeband im Rahmen der erfindungsgemäßen Verwendung von einer kreuzgewickelten Spule abgezogen; insbesondere erfolgt dieser Schritt automatisiert. Beispiele The adhesive tape according to the invention is likewise preferably pulled off a cross-wound reel within the scope of the use according to the invention; in particular, this step is automated. Examples
Testmethoden Test methods
Gelpermeationschromatographie zur Bestimmung des Molekulargewichts: Gel permeation chromatography to determine the molecular weight:
Die Angaben des Molekulargewichts in dieser Schrift beziehen sich auf die Bestimmung per Gelpermeationschromatographie. Die Bestimmung erfolgt an 100 mI klarfiltrierter Probe (Probenkonzentration 4 g/l). Als Eluent wird Tetrahydrofuran mit 0,1 Vol.-% Trifluoressigsäure eingesetzt. Die Messung erfolgt bei 25 °C. Als Vorsäule wird eine Säule Typ PSS-SDV, 5 m, 103 Ä, ID 8,0 mm 50 mm verwendet. Zur Auftrennung werden die Säulen des Typs PSS- SDV, 5 m, 103 Ä sowie 105Ä und 106 Ä mit jeweils ID 8,0 mm x 300 mm eingesetzt (Säulen der Firma Polymer Standards Service; Detektion mittels Differentialrefraktometer Shodex RI71). Die Durchflussmenge beträgt 1 ,0 ml pro Minute. Die Kalibrierung erfolgt gegen PMMA- Standards (Polymethylmethacrylat-Kalibrierung). The details of the molecular weight in this document relate to the determination by gel permeation chromatography. The determination is carried out on 100 ml clear-filtered sample (sample concentration 4 g / l). Tetrahydrofuran with 0.1% by volume of trifluoroacetic acid is used as the eluent. The measurement takes place at 25 ° C. A column type PSS-SDV, 5 m, 10 3 Å, ID 8.0 mm 50 mm is used as the guard column. The columns of the type PSS-SDV, 5 m, 10 3 Å as well as 10 5 Å and 10 6 Å, each with ID 8.0 mm x 300 mm, are used (columns from Polymer Standards Service; detection using a Shodex RI71 differential refractometer) . The flow rate is 1.0 ml per minute. The calibration is carried out against PMMA standards (polymethyl methacrylate calibration).
Wasserdurchlässigkeit: Water permeability:
Aus dem zu untersuchenden Klebeband wurden 5 mm schmale Streifen herausgeschnitten und auf einer quadratischen Metallplatte (Außenmaße 80 mm x 80 mm x 5 mm) aufgeklebt. Die Streifen wurden dabei so angeordnet, dass Sie eine geschlossene quadratische Kontur bilden. Dabei waren die Enden eines Streifens jeweils bündig mit der Seitenfläche des nächsten Streifenendes verbunden. 5 mm narrow strips were cut out of the adhesive tape to be examined and stuck onto a square metal plate (external dimensions 80 mm × 80 mm × 5 mm). The strips were arranged in such a way that they form a closed square contour. The ends of one strip were each connected flush with the side surface of the next end of the strip.
Im Inneren des Quadrats wurde anschließend eine Paste (KMn0 ) aufgetragen, die sich bei Kontakt mit Wasser deutlich Violett verfärbt. Eine identische Metallplatte wurde nun auf den Aufbau aufgelegt und verschraubt. Die Schrauben befanden sich außerhalb des Quadrats aus Klebebandstreifen. Durch 2 Stück je 1 mm starke Passscheiben wurde der Abstand der Metallplatten auf genau 2 mm eingestellt. Mit diesem Aufbau wurde sichergestellt, dass die wasserreaktive Paste in einem geschlossenen Raum innerhalb der Klebebandstreifen ist. Ein Eindringen von Wasser würde durch eine Verfärbung zu erkennen sein und auf Undichtigkeit des Klebebandes schließen lassen. A paste (KMn0) was then applied to the inside of the square, which turns a distinct purple color on contact with water. An identical metal plate was then placed on the structure and screwed. The screws were outside the square of strips of tape. The distance between the metal plates was set to exactly 2 mm by means of 2 pieces of 1 mm thick shim washers. This setup ensured that the water-reactive paste is in a closed space within the adhesive tape strips. A penetration of water would be recognizable by a discoloration and indicate a leak in the adhesive tape.
Die gesamte Probe wurde nun in ein Wasserbad gegeben, welches dann in einen Autoklav gelegt wurde. Zunächst wurde ein geringer Überdruck von 0,3 bar angelegt; in einer zweiten Prüfung simulierte ein Überdruck von 3 bar dann eine Wassersäule von 30 m. Nach 30-minütiger Lagerung unter Wasser im Autoklav wurde der Überdruck abgelassen, der Verbund entnommen und auf Verfärbung des KMnC>4 untersucht. Eine Verfärbung indiziert Wasserdurchlässigkeit des Klebebands, keine Verfärbung indiziert Dichtheit gegen Wasser (Ergebnis „wasserdurchlässig Ja/Nein“). The entire sample was then placed in a water bath, which was then placed in an autoclave. First, a slight overpressure of 0.3 bar was applied; In a second test, an overpressure of 3 bar then simulated a water column of 30 m. After 30 minutes' storage under water in the autoclave, the overpressure was released The composite was removed and examined for discoloration of the KMnC> 4. A discoloration indicates water permeability of the adhesive tape, no discoloration indicates impermeability to water (result “water permeable yes / no”).
Wiederablösbarkeit des verklebten Substrats (Simulation der Wiederablösung eines verklebten Batteriedeckels; reopenability): Re-detachability of the bonded substrate (simulation of the re-detachment of a bonded battery cover; reopenability):
Das Klebeband wurde mit der stärker klebenden Seite auf eine Aluminiumplatte (450 x 250 mm, 2,5 mm Dicke) in einem Abstand zum Plattenrand von 30 mm einmal umlaufend aufgebracht. Auf die freie Seite (von oben) wurde eine weitere Aluminiumplatte (450 x 250 mm, 1 mm Dicke) mit identischen Abmessungen aufgebracht. In die Fugen wurden auf jeder Seite 2 mm starke Passscheiben eingebracht, anschließend wurde der Verbund in einer Schraubzwinge zusammengepresst. Die Aluminiumplatten wurden danach miteinander verschraubt, indem in den Ecken der Platten zu diesem Zweck vorhandene Löcher genutzt wurden. The adhesive tape was applied with the more strongly adhesive side to an aluminum plate (450 × 250 mm, 2.5 mm thick) at a distance of 30 mm from the edge of the plate once all the way around. Another aluminum plate (450 x 250 mm, 1 mm thick) with identical dimensions was attached to the free side (from above). 2 mm thick shims were inserted into the joints on each side, then the composite was pressed together in a screw clamp. The aluminum plates were then screwed together using holes in the corners of the plates for this purpose.
Der so entstandene Verbund wurde für 10 Tage in einer Klimakammer bei 40 ° C und 100 % relativer Luftfeuchte gelagert. Nach der Entnahme wurde er für 24 h bei 23 °C und 50 % relativer Feuchte rekonditioniert. The composite formed in this way was stored for 10 days in a climatic chamber at 40 ° C. and 100% relative humidity. After removal, it was reconditioned for 24 hours at 23 ° C. and 50% relative humidity.
Anschließend wurden die Schrauben und Passscheiben entfernt und auf einer der kürzeren Seiten ein Spanngurt in die Fuge eingebracht, der mit einer Prüfmaschine (Zwick) verbunden war. Die obere (1 mm dicke) Platte wurde mit einer Geschwindigkeit von 300 mm/min in einem Winkel von 90 ° abgezogen, die dazu benötigte Maxi mal kraft wurde gemessen. In Tabelle 1 ist der Mittelwert aus drei Messungen angegeben. The screws and shims were then removed and a tensioning belt was inserted into the joint on one of the shorter sides and connected to a testing machine (Zwick). The upper (1 mm thick) plate was pulled off at a speed of 300 mm / min at an angle of 90 °, and the maximum force required for this was measured. Table 1 shows the mean value from three measurements.
Verwendete Klebebänder Adhesive tapes used
A - tesa® 61102 (geschlossenzelliger EPDM-Kautschuk-Schaum, einseitig mit einer Acrylat-Klebmasse beschichtet, Gesamtdicke 3.200 pm; tesa) A - tesa ® 61102 (closed-cell EPDM rubber foam, coated on one side with an acrylate adhesive, total thickness 3,200 μm; tesa)
B - tesa® ACXplus 70730 High Resistance (doppelseitiges Acrylat-B - tesa ® ACX plus 70730 High Resistance (double-sided acrylate
Schaumtape, beidseitig mit Acrylat- Haftklebmasse beschichtet, Gesamtdicke 2.900 gm; tesa), einseitig mit einer thermoplastischen Polyurethanfolie (Platilon® U04/PE, 30 gm; Bayer) laminiert Foam tape, coated on both sides with acrylate pressure-sensitive adhesive, total thickness 2,900 gm; tesa), laminated on one side with a thermoplastic polyurethane film (Platilon ® U04 / PE, 30 gm; Bayer)
C - tesa® ACXplus 70730 High Resistance, wobei die Acrylat-Haftklebmasse nur einseitig aufgebracht war, auf einer Seite also der Acrylatschaum freilag (siehe B, Gesamtdicke 2.850 pm; tesa) C - tesa ® ACX plus 70730 High Resistance, where the acrylate pressure-sensitive adhesive was only applied on one side, i.e. the acrylate foam was exposed on one side (see B, total thickness 2,850 μm; tesa)
D - tesa® 92111 HiP - High initial Performance, 3x auf sich selbst verklebt,D - tesa ® 92111 HiP - High initial performance, 3x glued to itself,
Gesamtdicke 3.300 pm; tesa); einseitig mit einer thermoplastischen Polyurethanfolie (Platilon® U04/PE, 30 pm; Bayer) laminiert Total thickness 3,300 pm; tesa); Laminated on one side with a thermoplastic polyurethane film (Platilon ® U04 / PE, 30 pm; Bayer)
E - tesa® ACXplus 70730 High Resistance (doppelseitiges Acrylat-Schaumtape, beidseitig mit Acrylat-Haftklebmasse beschichtet, Gesamtdicke 2.900 pm; tesa); Vergleichsbeispiel E - tesa ® ACX plus 70730 High Resistance (double-sided acrylate foam tape, coated on both sides with acrylate pressure-sensitive adhesive, total thickness 2,900 μm; tesa); Comparative example
Tabelle 1 : Testergebnisse Table 1: Test Results
Vgl. = Vergleichsbeispiel Compare = comparative example

Claims

Patentansprüche Claims
1. Klebeband mit unterschiedlicher Klebkraft auf beiden Hauptseiten, umfassend a) eine Polymerschaumschicht und b) eine äußere Haftklebmasseschicht und/oder eine äußere thermoplastische Folie auf jeweils einer Seite der Polymerschaumschicht; dadurch gekennzeichnet, dass sofern das Klebeband eine äußere Haftklebmasseschicht umfasst, es auf seiner mit der äußeren Haftklebmasseschicht ausgestatteten Seite eine höhere Klebkraft aufweist als auf der gegenüberliegenden Seite und/oder, sofern das Klebeband eine äußere thermoplastische Folie umfasst, es auf seiner mit der äußeren thermoplastischen Folie ausgestatteten Seite eine niedrigere Klebkraft aufweist als auf der gegenüberliegenden Seite. 1. Adhesive tape with different adhesive strength on both main sides, comprising a) a polymer foam layer and b) an outer pressure-sensitive adhesive layer and / or an outer thermoplastic film on each side of the polymer foam layer; characterized in that if the adhesive tape comprises an outer pressure-sensitive adhesive layer, it has a higher bond strength on its side equipped with the outer pressure-sensitive adhesive layer than on the opposite side and / or, if the adhesive tape comprises an outer thermoplastic film, it has a higher bond strength on its side with the outer thermoplastic film Film-equipped side has a lower adhesive strength than on the opposite side.
2. Klebeband gemäß Anspruch 1 , dadurch gekennzeichnet, dass die Polymerschaumschicht zu mindestens 35 Gew.-%, bezogen auf das Gesamtgewicht der Polymerschaumschicht, ein oder mehrere Polymere ausgewählt aus der Gruppe bestehend aus Polyolefinen; Polyurethanen; Polyvinylchlorid (PVC); Blends aus PVC und Nitrilkautschuk; Terpolymerisaten aus Ethylen, Propylen und einem nicht konjugierten Dien (EPDM); Copolymeren aus Ethylen und einem mit einer polaren Gruppe substituierten Ethylen; Blends aus Polyethylen und einem Polymer aus einem mit einer polaren Gruppe substituierten Ethylen; Poly(meth)acrylaten; Blends aus Poly(meth)acrylat und Synthesekautschuk sowie Gemischen aus zwei oder mehreren der vorstehend genannten Polymere enthält. 2. Adhesive tape according to claim 1, characterized in that the polymer foam layer comprises at least 35% by weight, based on the total weight of the polymer foam layer, of one or more polymers selected from the group consisting of polyolefins; Polyurethanes; Polyvinyl chloride (PVC); Blends of PVC and nitrile rubber; Terpolymers of ethylene, propylene and a non-conjugated diene (EPDM); Copolymers of ethylene and an ethylene substituted with a polar group; Blends of polyethylene and a polymer of an ethylene substituted with a polar group; Poly (meth) acrylates; Contains blends of poly (meth) acrylate and synthetic rubber and mixtures of two or more of the aforementioned polymers.
3. Klebeband gemäß einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass die Polymerschaumschicht mindestens ein Poly(meth)acrylat enthält. 3. Adhesive tape according to one of the preceding claims, characterized in that the polymer foam layer contains at least one poly (meth) acrylate.
4. Klebeband gemäß einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass die Polymerschaumschicht Mikroballons enthält. 4. Adhesive tape according to one of the preceding claims, characterized in that the polymer foam layer contains microballoons.
5. Klebeband gemäß einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass das Klebeband aus a) einer Polymerschaumschicht und b) einer äußeren Haftklebmasseschicht auf einer Seite der Polymerschaumschicht besteht. 5. Adhesive tape according to one of the preceding claims, characterized in that the adhesive tape consists of a) a polymer foam layer and b) an outer pressure-sensitive adhesive layer on one side of the polymer foam layer.
6. Klebeband gemäß einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass das Klebeband aus a) einer Polymerschaumschicht und b) einer äußeren thermoplastischen Folie auf einer Seite der Polymerschaumschicht besteht. 6. Adhesive tape according to one of claims 1 to 4, characterized in that the adhesive tape consists of a) a polymer foam layer and b) an outer thermoplastic film on one side of the polymer foam layer.
7. Klebeband gemäß einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass das Klebeband aus a) einer Polymerschaumschicht, b) einer äußeren Haftklebmasseschicht auf einer Seite der Polymerschaumschicht und c) einer äußeren thermoplastischen Folie auf der anderen Seite der Polymerschaumschicht besteht. 7. Adhesive tape according to one of claims 1 to 4, characterized in that the adhesive tape consists of a) a polymer foam layer, b) an outer pressure-sensitive adhesive layer on one side of the polymer foam layer and c) an outer thermoplastic film on the other side of the polymer foam layer.
8. Verwendung eines Klebebandes gemäß einem der Ansprüche 1 bis 7 zum Abdichten einer Verbindung zwischen zwei Bauteilen. 8. Use of an adhesive tape according to one of claims 1 to 7 for sealing a connection between two components.
9. Verwendung gemäß Anspruch 8, dadurch gekennzeichnet, dass die Verbindung zwischen den Bauteilen eine mechanisch bewirkte Verbindung ist. 9. Use according to claim 8, characterized in that the connection between the components is a mechanically effected connection.
EP21702168.2A 2020-01-15 2021-01-15 Sealing tape bonding weakly or not at all on one side Pending EP4090715A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102020200452.8A DE102020200452A1 (en) 2020-01-15 2020-01-15 Sealing tape weakly or non-adhesive on one side
PCT/EP2021/050796 WO2021144414A1 (en) 2020-01-15 2021-01-15 Sealing tape bonding weakly or not at all on one side

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US (1) US20230053665A1 (en)
EP (1) EP4090715A1 (en)
CN (1) CN114929824A (en)
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WO (1) WO2021144414A1 (en)

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Publication number Priority date Publication date Assignee Title
EP4086322A1 (en) * 2021-05-06 2022-11-09 3M Innovative Properties Company Multilayer pressure-sensitive adhesive foam tape
DE102023105238B3 (en) 2023-03-03 2024-03-28 Tesa Se Application device for the application of web-shaped adhesive elements

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Publication number Priority date Publication date Assignee Title
DE69430376T2 (en) * 1993-08-31 2002-11-14 Minnesota Mining & Mfg REMOVABLE FOAM ADHESIVE TAPE
DE202006016394U1 (en) * 2006-10-26 2008-02-21 K.M.B. Klebetechnik Gmbh Edge protection tape for protecting the edges of multiple glass panes, in particular fire protection panes, with sliding foil
JP5694777B2 (en) 2007-12-21 2015-04-01 スリーエム イノベイティブ プロパティズ カンパニー Multi-layer flushing tape
JP5919140B2 (en) * 2011-09-21 2016-05-18 日東電工株式会社 Ethylene / propylene / diene rubber foam and sealing material
DE102013209827A1 (en) * 2012-06-21 2013-12-24 Tesa Se Heat resistant tape
JP6734663B2 (en) * 2015-02-27 2020-08-05 日東電工株式会社 Double-sided adhesive tape
CN106349960A (en) * 2015-07-16 2017-01-25 德莎欧洲公司 Flame retardant foam tape
DE102016205822A1 (en) * 2016-04-07 2017-10-12 Tesa Se pressure-sensitive adhesive
DE102018200957A1 (en) * 2017-10-17 2019-04-18 Tesa Se Pressure-sensitive adhesive strip with partially foamed self-adhesive
DE102018208542A1 (en) * 2018-05-30 2019-12-05 Tesa Se Multilayer Adhesive Tape with Resin Modified Adhesive Adhesive
US11933040B2 (en) * 2018-06-04 2024-03-19 Gcp Applied Technologies Inc. Fish-mouth-resistant waterproofing membrane

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WO2021144414A1 (en) 2021-07-22
US20230053665A1 (en) 2023-02-23
CN114929824A (en) 2022-08-19

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